JP5361779B2 - Thermoplastic elastomer composition and foam obtained from the composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition and a foam obtained from the composition.

  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.

JP-A-6-73222 JP-A-9-143297

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

  The thermoplastic elastomer composition according to the present invention includes an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), an olefin resin (C1) having a functional group, and a metal compound. A thermoplastic elastomer composition comprising the kneaded product of (E), wherein the thermoplastic elastomer composition has a sea-island structure, and the island phase containing the olefin rubber (A) is a non-crosslinked olefin resin. Dispersed in a sea phase containing (B) and a kneaded product of a functional group-containing olefin resin (C1) and metal compound (E). The kneaded product is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). The presence of the ion-crosslinked olefin resin (C) is compared with the thermoplastic elastomer composition obtained without using the metal compound (E) in the thermoplastic elastomer composition obtained using the metal compound (E). This is indirectly proved from the fact that the melt tension increases.

  In the thermoplastic elastomer composition, the non-crosslinked olefin resin (B), the olefin resin (C1) having a functional group, and 100 parts by mass of at least a partially crosslinked olefin rubber (A) and The metal compound (E) kneaded product is included in a total amount of 2 to 200 parts by mass, and the functional group-containing olefin resin (C1) and metal compound (E) kneaded product and non-crosslinked olefin When the total amount of the resin and the resin (B) is 100 parts by mass, the kneaded product of the functional group-containing olefin resin (C1) and the metal compound (E) is 1 to 99 parts by mass, and the non-crosslinked type It is preferable that the olefin resin (B) is contained in an amount of 1 to 99 parts by mass.

  The olefin rubber (A) at least partially crosslinked is an ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained from ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. And an uncrosslinked olefin obtained by crosslinking at least one olefin rubber (A1) selected from ethylene and an α-olefin copolymer rubber obtained from ethylene and an α-olefin having 3 to 20 carbon atoms The resin (B) is preferably at least one olefin resin selected from propylene homopolymers, propylene copolymers, and ethylene copolymers.

  The softener (H) further includes an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), and an olefin having a functional group. 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 kneaded product of the system resin (C1) and the metal compound (E).

  The fluororesin (J) further includes an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), and an olefin having a functional group. It is preferably contained in an amount of 0.05 to 20 parts by mass with respect to 100 parts by mass in total with the kneaded processed product of the system resin (C1) and the metal compound (E).

  In the presence of the crosslinking agent (D) for crosslinking the olefin rubber (A1), the thermoplastic elastomer composition dynamically combines the olefin rubber (A1) and the non-crosslinked olefin resin (B). Heat-treating the olefin rubber (A1) into an olefin rubber (A) that is at least partially crosslinked, an olefin rubber (A) that is at least partially crosslinked, and a non-crosslinked olefin resin (B). A thermoplastic elastomer composition comprising a kneaded product of a functional group-containing olefin resin (C1) and a metal compound (E), the thermoplastic elastomer composition having a sea-island structure, and an olefin rubber ( A thermoplastic elastomer in which the island phase containing A) is dispersed in the sea phase containing the kneaded product of the olefin resin (C1) and the metal compound (E) and the non-crosslinked olefin resin (B) It is preferably obtained from the step [II] of producing a mer composition. The kneaded product is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). Thus, it is a preferable aspect that the olefin resin (C1) having a functional group and the metal compound (E) are an olefin resin (C) obtained by ion crosslinking. The presence of the ion-crosslinked olefin resin (C) is compared with the thermoplastic elastomer composition obtained without using the metal compound (E) in the thermoplastic elastomer composition obtained using the metal compound (E). This is indirectly proved from the fact that the melt tension increases.

  Here, the functional group-containing olefin resin (C1) is at least one olefin resin selected from maleic acid-modified propylene homopolymer, maleic acid-modified propylene copolymer, and maleic acid-modified ethylene copolymer. A resin is preferred.

  The method for producing a thermoplastic elastomer composition according to the present invention comprises an olefin rubber (A1) and a non-crosslinked olefin resin (B) in the presence of a crosslinking agent (D) for crosslinking the olefin rubber (A1). And the olefin rubber (A1) is an olefin rubber (A) that is at least partially crosslinked, and the olefin rubber (A) that is at least partially crosslinked and a non-crosslinked olefin system. Step [I] for producing a dynamically heat-treated product containing resin (B), the dynamically heat-treated product obtained in Step [I], an olefin resin (C1) having a functional group, and an olefin resin ( A metal compound (E) capable of reacting with the functional group of C1) is kneaded, and at least partially crosslinked olefinic rubber (A), non-crosslinked olefinic resin (B), and functionalized olefin Resin (C1 ) And a kneaded product of the metal compound (E), wherein the thermoplastic elastomer composition has a sea-island structure, and the island phase containing the olefin rubber (A) is olefin-based. A step [II] of producing a thermoplastic elastomer composition dispersed in a sea phase containing a kneaded product of the resin (C1) and the metal compound (E) and the non-crosslinked olefin resin (B). It is characterized by that. The kneaded product is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). Thus, it is a preferable aspect that the olefin resin (C1) having a functional group and the metal compound (E) are an olefin resin (C) obtained by ion crosslinking. The presence of the ion-crosslinked olefin resin (C) is compared with the thermoplastic elastomer composition obtained without using the metal compound (E) in the thermoplastic elastomer composition obtained using the metal compound (E). This is indirectly proved from the fact that the melt tension increases.

The molded product according to the present invention is characterized by comprising the thermoplastic elastomer composition.
The foaming thermoplastic elastomer composition according to the present invention is characterized by comprising the above thermoplastic elastomer composition and a foaming agent (K).

  In the foaming thermoplastic elastomer composition, the foaming agent (K) 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 agent (K) is preferably an inorganic or organic pyrolytic chemical foaming agent or a physical foaming agent.
The molded product according to the present invention is obtained from the thermoplastic elastomer composition for foaming.

The foam according to the present invention is obtained from the above thermoplastic elastomer composition for foaming.
The automobile part according to the present invention is characterized by comprising the above-mentioned foam.

  The building material which concerns on this invention consists of the said foam.

  According to the thermoplastic elastomer composition of the present invention, it is possible to produce a foam having a low specific gravity and excellent appearance, and also excellent balance between specific gravity and appearance and mechanical properties. Further, the foam of the present invention has a low specific gravity and an excellent appearance, and also has an excellent balance between the specific gravity and the appearance and mechanical properties.

FIG. 1 is a diagram for explaining the shape of a die used in the example.

Hereinafter, the present invention will be described in detail.
<Thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention comprises at least a partially crosslinked olefin rubber (A), a non-crosslinked olefin resin (B), an olefin resin (C1) having a functional group and a metal compound ( E) the kneaded product. The thermoplastic elastomer composition has a sea-island structure composed of an island phase and a sea phase. Specifically, the island phase containing the olefin rubber (A) comprises a non-crosslinked olefin resin (B) and a functional group. Is dispersed in a sea phase containing a kneaded product of the olefin resin (C1) and the metal compound (E).

  Here, the kneaded product is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). The kneaded product may contain the olefin resin (C1) having a functional group and the metal compound (E) as they are together with the crosslinked olefin resin (C). It is done.

  In the thermoplastic elastomer composition of the present invention, since the kneaded product is present in the sea phase, in other words, since the ionically crosslinked olefin resin (C) is present, the melt tension of the composition is increased, It is thought that the interface strength between the island and sea phases is also increasing. 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 mechanical characteristics.

  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.

  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. Of the olefin rubber (A), the cross-linked portion of the olefin rubber is mainly present in the island phase. The non-crosslinked olefin resin (B), the olefin resin (C1) having a functional group, and the metal compound It is considered that the kneaded product (E) is mainly dispersed in the sea phase.

  The olefin rubber (A) is at least partially cross-linked, and such cross-linking can be confirmed by measuring the gel content. 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 olefin-based resin (C1) is ionically crosslinked in the thermoplastic elastomer composition obtained without using the metal compound (E) in the thermoplastic elastomer composition obtained using the metal compound (E). In comparison, it can be confirmed indirectly since the melt tension increases.

  The olefin rubber (A) at least partially crosslinked is an ethylene / α-olefin / nonconjugated polyene copolymer rubber obtained from ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene, and It is preferably obtained by crosslinking at least one olefinic rubber (A1) selected from ethylene / α-olefin copolymer rubber obtained from ethylene and an α-olefin having 3 to 20 carbon atoms. Among these, at least a part of the olefin rubber (A) is preferably an ethylene / α-olefin / non-conjugated polyene copolymer rubber, because a foam having an appropriate crosslinked structure is obtained. It is preferably obtained by crosslinking an ethylene / propylene / non-conjugated polyene copolymer rubber, more preferably an ethylene / propylene / ethylidene norbornene copolymer rubber.

  The non-crosslinked olefin resin (B) is preferably at least one olefin resin selected from a propylene homopolymer, a propylene copolymer, and an ethylene copolymer.

  Further, the kneaded product of the functional group-containing olefin resin (C1) and the metal compound (E) specifically includes the functional group-containing olefin resin (C1) and the functional group of the olefin resin (C1). It is obtained from the metal compound (E) which can react. The functional group-containing olefin resin (C1) is at least one olefin resin selected from maleic acid-modified propylene homopolymer, maleic acid-modified propylene copolymer, and maleic acid-modified ethylene copolymer. It is preferable. The metal compound (E) is preferably a compound (E1) containing a divalent or higher valent metal ion or a compound (E2) having two or more functional groups neutralized with a metal ion. In the ion-crosslinked olefin resin (C) which is considered to be contained in the kneaded material, for example, the resin molecules are crosslinked via the metal ion of the compound (E1), or the resin molecules It is presumed that the space is cross-linked via an anion in which a metal ion is eliminated from the compound (E2).

  In the thermoplastic elastomer composition, the non-crosslinked olefin resin (B), the olefin resin (C1) having a functional group, and 100 parts by mass of at least a partially crosslinked olefin rubber (A) and It is preferable that the kneaded product of the metal compound (E) is contained in an amount of 2 to 200 parts by mass in total. Further, when the total of the non-crosslinked olefin resin (B), the kneaded product of the functional group-containing olefin resin (C1) and the metal compound (E) is 100 parts by mass, the non-crosslinked olefin resin It is preferable that the resin (B) is contained in an amount of 1 to 99 parts by mass, and the olefin-based resin (C1) having a functional group and the kneaded product of the metal compound (E) are contained in an amount of 1 to 99 parts by mass.

  The content of the kneaded product of the olefin rubber (A), the non-crosslinked olefin resin (B), the olefin resin (C1) having a functional group and the metal compound (E) at least partially crosslinked is When in the range, foaming of the foamed cells can be further suppressed when the foam is produced from the thermoplastic elastomer composition, and fine foamed cells can be more uniformly dispersed.

  The amount of the olefin rubber (A), the non-crosslinked olefin resin (B), and the kneaded material that are at least partially cross-linked can be determined from the amount charged when the thermoplastic elastomer composition is produced. it can. For example, when using the manufacturing method of the thermoplastic elastomer composition mentioned later, the quantity of the olefin rubber (A) in which at least a part of the composition is cross-linked is the olefin type used for the production of the thermoplastic elastomer composition. It can be regarded as corresponding to the total charge of rubber (A1), crosslinking agent (D) and crosslinking aid. The amount of the kneaded product in the composition can be considered to correspond to the total charge of the olefin resin (C1) having a functional group and the metal compound (E) used for the production of the thermoplastic elastomer composition.

  The thermoplastic elastomer composition of the present invention may further contain a softening agent (H), and the softening agent (H) comprises at least a partially crosslinked olefin rubber (A) and a non-crosslinked olefin. It is contained in an amount of 1 to 200 parts by mass with respect to a total of 100 parts by mass of the system resin (B) and the kneaded product of the functional group-containing olefin resin (C1) and metal compound (E). preferable. The softening agent (H) facilitates processing and assists the dispersion of carbon black and the like when preparing the thermoplastic elastomer composition. The softening agent (H) may be present in either the island phase or the sea phase.

  The thermoplastic elastomer composition of the present invention may further contain a fluororesin (J), and the fluororesin (J) is an olefin rubber (A) that is at least partially crosslinked, and a non-crosslinked olefin. It is contained in an amount of 0.05 to 20 parts by mass with respect to a total of 100 parts by mass of the system resin (B) and the kneaded product of the functional group-containing olefin resin (C1) and metal compound (E). It is preferable. The fluororesin (J) is used to increase the melt tension of the composition when a foam is produced from the thermoplastic elastomer composition. The fluororesin (J) is usually present in the sea phase.

  In addition, the thermoplastic elastomer composition of the present invention may contain a rubber (A ′) other than the olefin copolymer rubber (A) that is at least partially crosslinked within a range that does not impair the object of the present invention. . That is, the thermoplastic elastomer composition of the present invention may or may not contain the rubber (A ′). When the rubber (A ′) is included, it is usually included in a proportion 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 (A) that is at least partially crosslinked. Yes. The rubber (A ′) 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 comprises at least a partially crosslinked olefin rubber (A), a non-crosslinked olefin resin (B), a functional olefin resin (C1), and a metal. It is usually contained in a proportion of more than 0 parts by mass and 120 parts by mass or less, preferably 2 to 100 parts by mass with respect to 100 parts by mass in total with the compound (E) kneaded product. When the antioxidant is included, the antioxidant is at least partially crosslinked olefin rubber (A), non-crosslinked olefin resin (B), and olefin resin (C1) having a functional group. And it is contained in the ratio of 0.01-10 normally with respect to a total of 100 mass parts with the kneaded material of a metal compound (E). The additive may be present in either the island phase or the sea phase.

  In the thermoplastic elastomer composition, at least a partially crosslinked olefin rubber (A), a non-crosslinked olefin resin (B), and a softening agent (H) with respect to the total amount of the kneaded product, a fluororesin ( The amount of J) and other additives can be determined from the amount charged when the thermoplastic elastomer composition is produced. Here, for example, when using the method for producing a thermoplastic elastomer composition described later, an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), a kneaded product, Corresponds to the total charge of olefin rubber (A1), crosslinking agent (D), crosslinking aid, olefin resin (C1) and metal compound (E) used in the production of the thermoplastic elastomer composition. Then it can be considered. Further, the amount of the rubber (A ′) relative 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 (A1), the crosslinking agent (D) and the crosslinking aid.

<Method for producing thermoplastic elastomer composition>
The method for producing a thermoplastic elastomer composition of the present invention includes steps [I] and [II] described below. In other words, the thermoplastic elastomer composition of the present invention dynamically heat-treats the olefin rubber (A1) and the non-crosslinked olefin resin (B) in the presence of the cross-linking agent (D) to form a sea-island structure. A step of producing a dynamic heat-treated product, the above-mentioned dynamic heat-treated product, a non-crosslinked olefin resin (B) if necessary, an olefin resin (C1) having a functional group, and an olefin resin (C1). ) And the metal compound (E) capable of reacting with the functional group to produce a thermoplastic elastomer composition, more specifically, obtained by steps [I] and [II].

[Step [I]]
In the step [I], the olefin rubber (A1) and the non-crosslinked olefin resin (B) are dynamically heat-treated in the presence of a crosslinking agent (D) for crosslinking the olefin rubber (A1). A sea island comprising an olefinic rubber (A1), an olefinic rubber (A) that is at least partially crosslinked, and an olefinic rubber (A) that is at least partially crosslinked and a non-crosslinked olefinic resin (B) A dynamic heat-treated product having a structure is produced.

  The olefin rubber (A1) is an olefin copolymer rubber that crosslinks to reduce fluidity or does not flow by mixing with an organic peroxide and kneading under heating, for example. Also referred to as a system copolymer. In addition, when the olefin rubber (A1) is thermally reacted with the organic peroxide, a decomposition reaction and a crosslinking reaction occur. As a result of many crosslinking reactions, the olefin rubber (A1) in the dynamic heat-treated product Apparent molecular weight is thought to increase.

  As the olefin rubber (A1), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (amorphous random rubber) obtained by polymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene is used. 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. The olefin rubber (A1) 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, 1-octene and the like. 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 is obtained, it is 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 / non-conjugated polyene copolymer rubber and the ethylene / α-olefin copolymer rubber, the structural unit derived from ethylene is usually 40 to 85 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% is contained, and the structural unit derived from α-olefin is usually 60 to 15 mol%, preferably 45 to 15 mol%, more preferably 40 to 20 mol%. Here, the total of the structural unit derived from ethylene and the structural unit derived from α-olefin is 100 mol%.

  In the ethylene / α-olefin / non-conjugated polyene copolymer rubber, the copolymerization amount of the non-conjugated polyene is desirably 3 to 50, preferably 5 to 45, more 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 ethylene / α-olefin copolymer rubber and ethylene / α-olefin / non-conjugated polyene copolymer rubber, the intrinsic viscosity [η] measured in 135 ° C. decalin (decahydronaphthalene) is usually 0.8-6. 0.0 dl / g, preferably 1.0 to 5.0 dl / g, more preferably 1.1 to 4.0 dl / g.

  The ethylene / α-olefin copolymer rubber and the ethylene / α-olefin / non-conjugated polyene copolymer rubber having the above-mentioned characteristics are disclosed in “Polymer manufacturing process (issued by Industrial Research Co., Ltd.)”, 309-330. It can be prepared by a conventionally known method described on pages.

  Non-crosslinked olefinic resin (B) is an olefinic resin that decomposes and increases its fluidity, for example, by mixing with organic peroxide and kneading under heating, and is also an organic peroxide noncrosslinked olefinic polymer. Say. When the non-crosslinked olefin resin (B) is thermally reacted with the organic peroxide, a decomposition reaction and a crosslinking reaction occur. As a result of many decomposition reactions, the non-crosslinked olefin 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 olefin resin (B) include a propylene homopolymer, a propylene copolymer, and an ethylene copolymer. The non-crosslinked olefin 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 to 20, and more preferably 4 to 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. Of these, ethylene, 1-butene, and 1-octene are preferred as monomers to be copolymerized with propylene.

  The ethylene-based copolymer may contain more than 50 mass% of structural units derived from ethylene and 99 mass% or less, and structural units derived from α-olefins having 3 to 20 carbon atoms of 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 3-20, more preferably 3-10. Specific examples of the α-olefin include propylene, 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. 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 olefin 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 olefin resin (B) used in the step [I] will be described together with the step [II] described later.

Specifically, an organic peroxide is used as the crosslinking agent (D) for crosslinking the olefin rubber (A1).
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 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-butylperoxyisopropylcarbonate , Diacetyl organic peroxide, lauroyl organic peroxide, tert-butylcumyl organic peroxide, etc. An organic peroxide may be used independently or may use 2 or more types together.

  Among these, in terms of odor and scorch stability, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl -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 olefin resin (B), and the kneaded product in the amounts described above in the thermoplastic elastomer composition finally obtained. 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 (A1).

  In the present invention, in the crosslinking treatment with the organic peroxide, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitroso 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 olefinic rubber (A1) and the non-crosslinked olefinic resin (B), has an action of solubilizing the organic peroxide, and is an organic peroxide dispersant. 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 above-mentioned crosslinking aid is contained in the final amount of the thermoplastic elastomer composition so that the olefinic rubber (A), the non-crosslinked olefinic resin (B), and the kneaded product are included in the amounts described above. 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 (A1). 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 (A1) and the non-crosslinked olefin 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, a continuous mixer, etc., but 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 a softening agent (H). The softening agent (H) 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 (H), 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 its metal soap, pine oil, rosin or its derivatives, 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 Carbonic ester plasticizers, etc., other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. A softener (H) 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 (H) may be contained in the olefin rubber (A1) that has been oil-extended in advance.
The amount of the softening agent (H) 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 a rubber (A ′) other than the olefin copolymer rubber (A) as long as the object of the present invention is not impaired. Examples of such rubber (A ′) include diene rubbers such as styrene / butadiene rubber (SBR), nitrile rubber (NBR), and natural rubber (NR), and silicon rubber. As the rubber (A ′), 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. The rubber (A ′) 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.

  The rubber (A ′) is preferably used so as to be contained in the above-mentioned amount in the thermoplastic elastomer composition finally obtained. 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 (A1).

  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 (A1) becomes an olefin rubber (A) that is at least partially crosslinked. Then, a dynamic heat-treated product having a sea-island structure including the olefin rubber (A) and the non-crosslinked olefin resin (B) at least partially crosslinked is produced. 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, the value obtained by subtracting the weight of the cyclohexane-soluble component other than the polymer component (for example, softener) and the weight of the 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 olefin resin (B). . Specifically, the portion of the olefin rubber (A) that has been crosslinked to form crosslinked particles is mainly present in the island phase, and the non-crosslinked olefin 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]]
Step [II] includes a dynamically heat-treated product having a sea-island structure obtained in Step [I], a non-crosslinked olefin resin (B) as necessary, and an olefin resin (C1) having a functional group. A metal compound (E) that can react with a functional group of the olefin resin (C1), an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), A thermoplastic elastomer composition containing a kneaded product of the functional group-containing olefin resin (C1) and metal compound (E) is produced. The thermoplastic elastomer composition has a sea-island structure, and the island phase containing the olefinic rubber (A) comprises a non-crosslinked olefinic resin (B), an olefinic resin (C1) having a functional group, and a metal compound ( It is thought that it is dispersed in the sea phase containing the kneaded product of E). In addition, the olefin resin (C1) and the metal compound (E) are considered to be an ionically crosslinked olefin resin (C) by the above-described process. In other words, the kneaded product obtained in step [II] is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). In addition, the olefin resin (C1) having all functional groups may not be a crosslinked olefin resin (C) by the kneading, and the kneaded product may contain a crosslinked olefin resin (C ) And a functional group-containing olefin resin (C1) and metal compound (E) may be included as they are.

  As the olefin resin (C1) containing a functional group, an olefin resin obtained by modifying the propylene homopolymer, propylene copolymer or ethylene copolymer described in the non-crosslinked olefin resin (B) with a functional group. Resin. Specifically, it is an olefin resin obtained by graft-modifying the above polymer with a functional group-containing compound such as an acid or a derivative thereof.

  Examples of the acid or derivatives thereof include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (registered trademark; nadic acid (endocis-bicyclo [2,2,1] hept -2-ene-5,6-dicarboxylic acid), unsaturated carboxylic acids such as acrylic acid and methacrylic acid and their anhydrides, sulfonic acids and derivatives thereof, imides, amides, and esters.

  Specific examples of the acid derivatives include anhydrides of unsaturated carboxylic acids such as maleic acid, citraconic acid and nadic acid (registered trademark), maleimide, monomethyl maleate, glycidyl maleate, and sulfonic acid anhydride. Can be mentioned. Among these, unsaturated carboxylic acid anhydrides are preferable, and maleic acid and nadic acid (registered trademark) acid anhydrides are more preferable. Therefore, as the olefin resin (C1) containing a functional group, a maleic acid-modified propylene homopolymer, a maleic acid-modified propylene copolymer, and a maleic acid-modified ethylene copolymer are preferably used. The olefin resin (C1) containing a functional group may be used alone or in combination of two or more.

  As a method for obtaining an olefin resin (C1) containing a functional group by graft-modifying the olefin resin with a functional group-containing compound, a conventionally known method can be used without any particular limitation. For example, a melt modification method in which a functional group-containing compound is added to a melted olefin resin and graft copolymerized, or a solution modification in which the olefin resin is dissolved in a solvent and then a functional group-containing compound is added and graft copolymerized. Law.

  In order to obtain an olefin resin (C1) containing a functional group by efficiently grafting a functional group-containing compound onto the olefin resin, the reaction is usually performed at a temperature of 60 to 350 ° C. in the presence of a radical initiator. Is preferred. The usage-amount of a radical initiator is 0.001-2 mass parts normally with respect to 100 mass parts of olefin resin.

  Here, as the radical initiator, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl- And organic peroxides such as 2,5-di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene.

  The amount of the functional group contained in the functional group-containing olefin resin (C1) is preferably 0.01 to 50% by weight, more preferably 0.05 to 40% by weight in the functional group-containing olefin resin (C1). %, More preferably 0.1 to 30% by weight.

  In the step [II], the olefin resin (C1) containing a functional group is obtained from the olefin rubber (A), the non-crosslinked olefin resin (B) and the kneading treatment in the thermoplastic elastomer composition finally obtained. What is necessary is just to use so that a thing may be contained in the quantity mentioned above. For example, the olefin resin (C1) containing a functional group is preferably used in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the olefin rubber (A1) used in the step [I].

  The metal compound (E) capable of reacting with the functional group of the olefin resin (C1) reacts with the functional group contained in the olefin resin (C1) regardless of whether it is reversible or irreversible. It is a compound capable of forming a bridge between C1) and the metal compound (E). In the above thermoplastic elastomer composition obtained using the metal compound (E), the melt tension is increased in the above-described thermoplastic elastomer composition obtained without using the metal compound (E). It is suggested. Since the metal compound (E) crosslinks between the molecules of the olefin resin (C1), the metal compound (E) is specifically neutralized with a compound (E1) containing a metal ion having a valence of 2 or more or a metal ion. It is preferable that it is a compound (E2) which has 2 or more of the made functional groups.

In the compound (E1) containing divalent or higher metal ions, the divalent or higher metal ions include Cu ²⁺ , Mg ²⁺ , Ba ²⁺ , Zn ²⁺ , Al ³⁺ , Fe ³⁺ , Sn ^2+. , Ca ²⁺ , Ti ⁴⁺ , Zr ⁴⁺ .

Examples of the compound (E1) containing a divalent or higher metal ion include metal oxides, metal hydroxides, metal salts of organic acids, and metal salts of inorganic acids.
Specific examples of the metal oxide include CuO, MgO, BaO, ZnO, Al ₂ O ₃ , Fe ₂ O ₃ , SnO, CaO, TiO ₂ and ZrO ₂ . Specific examples of the metal hydroxide include Cu (OH) ₂ , Cu ₂ O (OH) ₂ , Mg (OH) ₂ , Mg ₂ O (OH) ₂ , Ba (OH) ₂ , and Zn (OH) _2. , Sn (OH) ₂ and Ca (OH) ₂ .

  Examples of the organic acid include stearic acid, acetic acid, and carbonic acid, and the metal salt of the organic acid is the metal salt of the organic acid, specifically, calcium stearate, zinc stearate, and zinc acetate.

  Examples of the inorganic acid include phosphoric acid, boric acid, nitric acid, hydrofluoric acid, hydrochloric acid, chromic acid, hydrobromic acid, hypochlorous acid, and perchloric acid. Specific examples of the metal salt include barium nitrite, calcium phosphite, calcium chloride, magnesium chloride, and aluminum chloride.

In the compound (E2) having two or more functional groups neutralized with metal ions, monovalent metal ions are preferably used as the metal ions, and specific examples include Li ⁺ , Na ⁺ and K ^+. It is done.

  Examples of the compound (E2) having two or more functional groups neutralized with metal ions include metal salts of organic acids. Here, the functional group in the compound (E2) is preferably a carboxyl group.

  Organic acids include succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, iminodiacetic acid, citric acid, nitrilotriacetic acid, hemimellitic acid, trimellitic acid, trimesic acid, butanetetracarboxylic acid, ethylenediaminetetraacetic acid, merophane Acid, planitic acid, pyroperic acid, diethylenetriaminepentaacetic acid, melittic acid, and the metal salt of organic acid is a metal salt of the above organic acid, specifically potassium succinate, potassium iminodiacetate, potassium citrate, Examples include potassium nitrilotriacetate, potassium ethylenediaminetetraacetate, and potassium diethylenetriaminepentaacetate.

These metal compounds (E) may be used independently or may use 2 or more types together. The metal compound (E) may be prepared using a conventionally known method, or a commercially available product may be used.
In the step [II], the metal compound (E) is an amount of the olefin rubber (A), the non-crosslinked olefin resin (B) and the kneaded product in the final thermoplastic elastomer composition. What is necessary is just to use so that it may be contained. For example, it is preferable that a metal compound (E) is used in the quantity of 0.05-20 mass parts with respect to 100 mass parts of olefin resin (C1) containing a functional group.

  As the non-crosslinked olefin resin (B) used as necessary, the same one as in step [I] is used, and the preferred range is also the same. The non-crosslinked olefin 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. However, when the non-crosslinked olefin 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 olefin 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 olefin 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 olefin resin (B) is used only in the step [I], the amount of 1 to 100 parts by mass with respect to 100 parts by mass of the olefin rubber (A1) used in the step [I]. It is preferable to mix | blend with. Alternatively, when used in both steps [I] and [II], the total amount in steps [I] and [II] is 100 parts by mass of the olefin rubber (A1) used in step [I]. It is preferable to mix | blend so that it may become 1-100 mass parts.

  In step [II], the dynamically heat-treated product obtained in step [I], if necessary, a non-crosslinked olefin resin (B), an olefin resin (C1) having a functional group, and an olefin resin The metal compound (E) capable of reacting with the functional group (C1) is kneaded, preferably melt kneaded.

  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 (H). The softening agent (H) 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 softener (H), the same one as in step [I] is used, and the preferred range is also the same.

  The softening agent (H) may be used only in step [I] or [II] as described above, or may be used in both steps [I] and [II]. In any case, the blending amount of the softening agent (H) may be used so as to be included in the amount described above in the finally obtained thermoplastic elastomer composition. For example, when the softener (H) is used only in the step [I] or [II], the olefin rubber (A1), the non-crosslinked olefin 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 the olefin resin (C1) which has a functional group. Alternatively, when used in both steps [I] and [II], the olefin rubber (A1), non-crosslinked olefin resin (B) used in steps [I] and [II], and an olefin having a functional group 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 of resin (C1).

  The kneading process may be performed by further blending the fluororesin (J). When the fluororesin (J) is used, when a 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 (J), polytetrafluoroethylene is preferably used.

  What is necessary is just to use the compounding quantity of a fluororesin (J) so that it may be contained by the quantity mentioned above in the thermoplastic elastomer composition finally obtained. For example, the fluororesin (J) is 100 masses in total of the olefin rubber (A1), the non-crosslinked olefin resin (B) and the olefin resin (C1) having a functional group used in the steps [I] and [II]. It is preferable to mix | blend so that it may become more than 0 mass part and 20 mass parts or less with respect to a part.

  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 (A1), the non-crosslinked olefin resin (B) and the functional group used in the steps [I] and [II] are used. It is preferable to mix | blend so that the quantity in process [I] or [II] may exceed 0 mass part and will be 120 mass parts or less with respect to a total of 100 mass parts of the olefin resin (C1) to have. Alternatively, when used in both steps [I] and [II], the olefin rubber (A1), non-crosslinked olefin resin (B) used in steps [I] and [II], and an olefin having a functional group It is preferable that the total amount in the steps [I] and [II] is more than 0 parts by mass and 120 parts by mass or less based on 100 parts by mass of the resin (C1).

  As described above, the antioxidant may be used only in step [I] or [II], or may be used in both 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 (A1), the non-crosslinked olefin resin (B) and the functional group used in the steps [I] and [II]. It is preferable to mix | blend so that the quantity in process [I] or [II] may be 0.01-10 mass parts with respect to a total of 100 mass parts of olefin resin (C1) which has this. Alternatively, when used in both steps [I] and [II], the olefin rubber (A1), non-crosslinked olefin resin (B) used in steps [I] and [II], and an olefin having a functional group 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 of resin (C1).

  By kneading in the step [II], the olefin resin (C1) is considered to be an olefin resin (C) ion-crosslinked with the metal compound (E). In other words, the kneaded product obtained in step [II] is considered to contain an olefin resin (C) obtained by ion-crosslinking an olefin resin (C1) having a functional group with a metal compound (E). The ionic crosslinking means that the functional group of the olefin resin reacts with the compound (E1) by kneading, and the molecules of the olefin resin are crosslinked via the metal ion of the compound (E1), or the olefinic system. It means that the functional group of the resin reacts with the compound (E2), and the molecules of the olefin resin are cross-linked via an anion in which the metal ion is eliminated from the compound (E2). In addition, it is thought that all the molecules of the olefin resin (C1) may not be crosslinked by kneading. In other words, the olefin resin (C1) having all functional groups may not be crosslinked olefin resin (C) by the kneading, and the kneaded product may contain a crosslinked olefin resin ( It is considered that the olefin resin (C1) having a functional group and the metal compound (E) may be contained as they are together with C).

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 rubber (A) has a non-crosslinked olefin resin (B) and a functional group. It is thought that it is dispersed in the sea phase containing the olefin resin (C1) and the kneaded product of the metal compound (E). In this kneaded material, the olefin resin (C1) is considered to be an olefin resin (C) ionically crosslinked with the metal compound (E).
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. Of the olefin rubber (A), the cross-linked cross-linked portion is mainly present in the island phase, and the non-cross-linked olefin resin (B), the olefin resin (C1) having a functional group, and the metal compound It is considered that the kneaded product (E) 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 ion-crosslinked olefin resin (C) is compared with the thermoplastic elastomer composition obtained without using the metal compound (E) in the thermoplastic elastomer composition obtained using the metal compound (E). Thus, it can be confirmed indirectly because the melt tension increases.

  As described above, the non-crosslinked olefin resin (B) is blended in the step [II] as necessary in addition to the step [I]. The molecules of the non-crosslinked olefin 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 olefin 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 said kneaded material exists in a sea phase, it is not good. Therefore, 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 and foam for foaming>
The foaming thermoplastic elastomer composition of the present invention comprises the above-described thermoplastic elastomer composition and a foaming agent (K). A foam can be obtained from this thermoplastic elastomer composition for foaming.

Examples of the foaming agent (K) 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 blowing agents include nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine;
Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate;
Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide;
And 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 in the thermoplastic elastomer composition in a supercritical state from the viewpoint of rapid and uniform mixing and finer bubbles.

The foaming agent (K) 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, ethylenediaminetetraacetic acid, triethylenetetramine hexaacetic acid, nitrilolic acid and other polycarboxylic acids and carbonic acid Mixtures of inorganic carbonate compounds such as sodium hydrogen, sodium aluminum hydrogen carbonate, potassium hydrogen carbonate, and intermediates produced by these reactions, for example, salts of polycarboxylic acids such as sodium dihydrogen citrate and potassium oxalate;
Nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine;
Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate;
Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide;
And azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Among these, calcium stearate and ethylene tetrafluoride resin fine powder are particularly preferable.

  The addition amounts of the foam-forming nucleating agent and the wetting agent are each preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the thermoplastic elastomer composition. .

  When preparing a foam using a pyrolytic chemical foaming agent, for example, a pelletized thermoplastic elastomer composition, a pyrolytic chemical foaming agent made into a pellet form 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 the balance between specific gravity and 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, weather strip sponges, body panels, steering wheels, side shields, and other automotive parts; ground improvement sheets, water plates, noise prevention walls, and other civil engineering materials and building materials ; Footwear such as shoe soles and sandals; Electrical parts such as electric wire coverings, connectors, cap plugs; Leisure goods such as golf club grips, baseball bat grips, swimming fins, underwater glasses; gaskets, waterproof cloths, garden hoses, belts, Examples include miscellaneous goods such as draining sheets and cosmetic puffs.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, the molding of foams in the examples and evaluation of basic physical properties 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 a shape as 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 molding equipment: 100-ton automatic heating automatic 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 at 230 ° C., 2.16 kg, 5 kg load or 10 kg load by the method of ASTM-D-1238-65T.

(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 room 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 x 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.

[Measurement of foam appearance]
The appearance of the foam was determined at the following level by confirming the appearance of the extruded round one foam. As a product, level 3 or higher is acceptable.
Level 5: The cells of the foam are fine and uniform. The surface state is smooth and has no irregularities.
Level 4: The foam cells are fine and relatively uniform. The surface state is smooth although there are some irregularities.
Level 3: The cells of the foam have a distribution in particle diameter, and the surface state is somewhat smooth, although there are some irregularities.
Level 2: There is a particle size distribution of the foam cell, and there is a part where the foam is broken. The surface condition is slightly uneven, which is a level of failure as a product.
Level 1: The foam cell has a large particle size, and the shape of the foam cannot be maintained. The surface state is a level that has large irregularities and does not deserve physical property evaluation.

[Example 1-1]
<Kneading 1> Preparation of dynamic heat-treated product 1 (see Table 1)
To 100 parts by mass of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber having an ethylene content of 69 mol%, an iodine value of 20, and an intrinsic viscosity [η] of 4.1 dl / g, a mineral oil softener ( Paraffinic oil PW-380; Idemitsu Kosan Dyna Process Oil) 48 parts by mass of oil-extended EPT (4100E) 36 parts by mass; ethylene content 75.9 mol%, iodine value 11.5, limiting viscosity 3.4 dl Oil-extended EPT (3072 EPM) in which 100 parts by mass of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber / g is 40 parts by mass of paraffinic oil; -D-1238-65T, 230 ° C., 2.16 kg load) is 2.0 g / 10 min. 11 parts by mass of polypropylene (F704NP; manufactured by Prime Polymer); paraffin Oil (PW-100; Idemitsu Kosan Dynas Process Oil) 18 parts by mass; butyl rubber (BT-101SNT; manufactured by Exxon) 4 parts by mass; and silicon rubber (BY27-002; manufactured by Toray Dow Corning Silicone) 2 In a mixture of parts by mass (pellet shape), 1.04 parts by mass of a crosslinking agent 1,3-bis (tert-butylperoxyisopropyl) benzene (Perhexa 25B) and 0.42 parts by mass of a crosslinking aid divinylbenzene (DVB-810) And 2.08 parts by mass of a mixed solution of paraffinic oil (PW-100) and the antioxidant tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] 0.1 parts by mass of methane (Irganox 1010) is mixed with a 75 L Henschel mixer (FM75-J; manufactured by Mitsui Mining Co., Ltd.), and a crosslinking agent, a crosslinking aid and an antioxidant are added to the pellet surface. To obtain a mixture obtained by wearing.

  Next, the mixture and 21 parts by mass of paraffinic oil (PW-100) were mixed at a cylinder temperature of 120 to 200 ° C. and a die temperature of 200 using a twin-screw mixing extruder (HyperKTX-46 manufactured by Kobe Steel). Melting and kneading, that is, dynamic thermal cross-linking treatment at a processing temperature of ℃, rotation speed of 400 rpm and extrusion rate of 60 kg / hr, dynamic heat treated product 1 (part where dispersed particles of cross-linked EPT are uniformly dispersed in PP) Cross-linked thermoplastic elastomer composition).

なお、表１中、ＥＰＴは、エチレン・プロピレン・５―エチリデン−２−ノルボルネン共重合体ゴムを表し、ＰＰはポリプロピレンを表す。

In Table 1, EPT represents ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber, and PP represents polypropylene.

<Kneading 2-1> Preparation of thermoplastic elastomer composition 2-1 (see Table 2)
Next, polypropylene (propylene copolymer, B241) having a melt flow rate of 0.5 g / 10 min was added to 93.6 parts by mass of the obtained dynamic heat-treated product 1 (partially crosslinked thermoplastic elastomer composition). Manufactured by Prime Polymer Co., Ltd.) 0.6 parts by mass, polypropylene having a melt flow rate of 3.0 g / 10 min (propylene copolymer, VP103W; manufactured by Prime Polymer Co.) 1.9 parts by mass, and maleic acid-modified polypropylene (Maleic acid-modified propylene polymer, GR-2; manufactured by Mitsui Chemicals Co., Ltd.) 0.6 parts by mass, fatty acid metal salt (zinc stearate; manufactured by Sakai Chemical Co., Ltd.) 0.1 parts by mass, and fluon (polytetrafluoroethylene) PTFE G355; manufactured by Asahi Glass Co., Ltd.) 1.15 parts by mass and carbon black masterbatch (PE4993; manufactured by CABOT Co., Ltd.) 3.3 quality 23.6 parts by weight of paraffinic oil (PW-100) and the antioxidant tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ] 0.1 parts by mass of methane (Irganox 1010) was melt kneaded under the same conditions as kneading 1 using a kneading 1 shaft extruder to obtain the desired olefinic thermoplastic elastomer composition 2-1.
Various physical properties were evaluated using the thermoplastic elastomer composition 2-1 obtained in the kneading 2-1. The results are shown in Table 3.

[Example 2-1]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-1, 3.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foaming nucleating agent (synthetic machine synthesis) (Made by company) 0.1 parts by mass dry blended, using an extrusion foam molding apparatus (Nagata Manufacturing Co., Ltd.), cylinder temperature 150-220 ° C, die temperature 170 ° C, rotation speed 25 rpm, resin pressure 12.5 MPa, Extrusion molding was performed in a round shape at a take-up speed of 7.1 m / min and an Air flow rate of 0.8 L / min to obtain a round-shaped foam molded body (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-2]
<Kneading 2-2> Preparation of thermoplastic elastomer composition 2-2 (see Table 2)
In kneading 2-1, it was carried out in the same manner as kneading 2-1, except that maleic acid-modified polypropylene (GR-2; manufactured by Mitsui Chemicals) was changed to Q3000 (maleic acid-modified propylene polymer, manufactured by Mitsui Chemicals). .
Using the thermoplastic elastomer composition 2-2 obtained by kneading 2-2, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Example 2-2]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-2, 3.5 parts by mass of a foaming agent (bicarbonate-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-3]
<Kneading 2-3> Preparation of thermoplastic elastomer composition 2-3 (see Table 2)
In the kneading 2-1, ethylene as a comonomer is copolymerized by 4.5% by mass and the amount of polypropylene (B241; manufactured by Prime Polymer Co., Ltd.) having a melt flow rate of 0.5 g / 10 min is 0.4 parts by mass. The amount of polypropylene (VP103W; manufactured by Prime Polymer) with a flow rate of 3.0 g / 10 min is 1.2 parts by mass, instead of 0.6 parts by mass of maleic acid-modified polypropylene (GR-2; manufactured by Mitsui Chemicals). Was carried out in the same manner as kneading 2-1, except that 1.5 parts by mass of Q3000 (Mitsui Chemicals) was used.
Using the thermoplastic elastomer composition 2-3 obtained by kneading 2-3, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Example 2-3-3-A]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained in the kneading 2-3, 3.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.) and calcium stearate as a foaming nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 2-3-3-B]
In Example 2-3-3-A, a round foam-shaped molded article was obtained in the same manner as Example 2-3-3-A, except that the foaming agent was changed to 4.5 parts by mass (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-4]
<Kneading 2-4> Preparation of thermoplastic elastomer composition 2-4 (see Table 2)
In the kneading 2-1, similar to the kneading 2-1, except that a maleic acid-modified ethylene resin (MH7020; manufactured by Mitsui Chemicals) was used instead of maleic acid-modified polypropylene (GR-2; manufactured by Mitsui Chemicals). went.
Using the thermoplastic elastomer composition 2-4 obtained by kneading 2-4, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Example 2-4]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-4, 4.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foam molded product was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-5]
<Kneading 2-5> Preparation of thermoplastic elastomer composition 2-5 (see Table 2)
In kneading 2-1, a polypropylene having a melt flow rate of 0.5 g / 10 min and a polypropylene having a melt flow rate of 3.0 g / 10 min were not used, but a maleic acid-modified polypropylene (GR-2; manufactured by Mitsui Chemicals, Inc.) The amount was adjusted to 2.2 parts by mass, and the amount of zinc stearate (fatty acid metal salt; manufactured by Sakai Chemical Co., Ltd.) was changed to 0.15 parts by mass.
Using the thermoplastic elastomer composition 2-5 obtained by kneading 2-5, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Example 2-5]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-5, 3.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foaming nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-6]
<Kneading 2-6> Preparation of thermoplastic elastomer composition 2-6 (see Table 2)
In the kneading 2-1, the amount of polypropylene (B241; manufactured by Prime Polymer Co., Ltd.) having a melt flow rate of 0.5 g / 10 min is 0.3 parts by mass, and the polypropylene (VP103W) has a melt flow rate of 3.0 g / 10 min. The amount of maleic acid-modified ethylene resin (GR-2; manufactured by Mitsui Chemicals) is 2.2 parts by mass, and zinc stearate (fatty acid metal salt; The amount was 0.15 parts by mass and the same as Kneading 2-1, except that fluon (polytetrafluoroethylene PTFE G355; manufactured by Asahi Glass Co., Ltd.) was not used.
Using the thermoplastic elastomer composition 2-6 obtained by kneading 2-6, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Example 2-6]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-6, 3.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-7]
<Kneading 2-7> Preparation of thermoplastic elastomer composition 2-7 (see Table 2)
In kneading 2-1, polypropylene (propylene copolymer, B241; manufactured by Prime Polymer Co., Ltd.) was converted to polypropylene (propylene copolymer, F744NP; manufactured by Prime Polymer Co., Ltd.) having a melt flow rate of 7.0 g / 10 min. The procedure was the same as kneading 2-1, except that the maleic acid-modified polypropylene (GR-2; manufactured by Mitsui Chemicals) was changed to Q3000 (manufactured by Mitsui Chemicals).
Various physical properties were evaluated in the same manner as in Example 1-1 by using the thermoplastic elastomer composition 2-7 obtained by kneading 2-7. The results are shown in Table 3.

[Example 2-7]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-7, 4.5 parts by mass of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) was dry blended to obtain a round-shaped foamed molded product in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Example 1-8]
<Kneading 2-8> Preparation of thermoplastic elastomer composition 2-8 (see Table 2)
In kneading 2-1, it was performed in the same manner as kneading 2-1, except that zinc oxide (manufactured by Hakushitec) was used instead of zinc stearate.
Various physical properties were evaluated in the same manner as in Example 1-1 using the thermoplastic elastomer composition 2-8 obtained by kneading 2-8. The results are shown in Table 3.

[Example 2-8]
Per 100 parts by mass of the olefinic thermoplastic elastomer composition obtained by kneading 2-8, 3.5 parts by mass of a foaming agent (bicarbonate-type EE385; manufactured by Eiwa Kasei Co., Ltd.) and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) was dry blended to obtain a round-shaped foamed molded product in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Comparative Example 1-1]
<Kneading 2-9> Preparation of thermoplastic elastomer composition 2-9 (see Table 2)
In the kneading 2-1, the amount of polypropylene (B241; manufactured by Prime Polymer Co., Ltd.) having a melt flow rate of 0.5 g / 10 min was 0.7 parts by mass, and the polypropylene (VP103W) had a melt flow rate of 3.0 g / 10 min. ; Prime Polymer Co., Ltd.) was 2.4 parts by mass, and the same procedure as in Kneading 2-1 was performed except that maleic acid-modified polypropylene and zinc stearate were not used.
Using the thermoplastic elastomer composition 2-9 obtained by kneading 2-9, various physical properties were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[Comparative Example 2-1-A]
Per 100 parts by mass of the olefin-based thermoplastic elastomer composition obtained by kneading 2-9, 3.5 parts by mass of a foaming agent (bicarbonate-type EE385; manufactured by Eiwa Kasei Co., Ltd.) and calcium stearate as a foam nucleating agent (Three-sharing machine synthesis) 0.1 parts by mass) were dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Comparative Example 2-1-B]
In Comparative Example 2-1-A, a round foam-shaped molded article was obtained in the same manner as Comparative Example 2-1-A, except that the foaming agent was changed to 4.5 parts by mass (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Comparative Example 1-2]
<Kneading 2-10> Preparation of thermoplastic elastomer composition 2-10 (see Table 2)
In kneading 2-1, in place of 0.6 parts by mass of polypropylene B241 (manufactured by Mitsui Chemicals) and 1.9 parts by mass of polypropylene VP103W (manufactured by Prime Polymer), polypropylene having a melt flow rate of 7.0 g / 10 min ( Propylene copolymer, F744NP (manufactured by Prime Polymer Co., Ltd.) was used in the same manner as kneading 2-1, except that 3.1 parts by mass and maleic acid-modified polypropylene and zinc stearate were not used.
Various physical properties were evaluated in the same manner as in Example 1-1 using the thermoplastic elastomer composition 2-10 obtained by kneading 2-10. The results are shown in Table 3.

[Comparative Example 2-2]
Kneading 2-10 Per 100 parts by mass of the obtained olefinic thermoplastic elastomer composition, 3.5 parts by mass of a foaming agent (bicarbonate-type EE385; manufactured by Eiwa Kasei Co., Ltd.), and calcium stearate as a foaming nucleating agent (Sansha Co., Ltd.) (Product made) 0.1 parts by mass was dry blended, and a round-shaped foamed molded article was obtained in the same manner as in Example 2-1 (see Table 4).
Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

なお、表２中、ＰＰはポリプロピレンを表し、ＥＢＲはエチレン・ブテン共重合体を表す。

In Table 2, PP represents polypropylene, and EBR represents an ethylene / butene copolymer.

Claims (15)

An olefin rubber (A) that is at least partially crosslinked;
A non-crosslinked olefin resin (B);
A thermoplastic elastomer composition comprising a kneaded product of a functional group-containing olefin resin (C1) and a metal compound (E),
The olefin resin (C1) having a functional group is at least one olefin resin selected from maleic acid-modified propylene homopolymer, maleic acid-modified propylene copolymer, and maleic acid-modified ethylene copolymer. ,
The thermoplastic elastomer composition has a sea-island structure, and the island phase containing the olefin rubber (A) is a kneaded product of the olefin resin (C1) and metal compound (E) having a functional group, and a non-crosslinked type A thermoplastic elastomer composition which is dispersed in a sea phase containing an olefin resin (B). With respect to 100 parts by mass of at least a partially crosslinked olefin rubber (A), a kneaded product of a functional group-containing olefin resin (C1) and metal compound (E), and a non-crosslinked olefin resin (B) ) In a total amount of 2 to 200 parts by weight,
Olefin resin having a functional group when the total of the olefin resin (C1) having a functional group (C1) and the metal compound (E) and the non-crosslinked olefin resin (B) is 100 parts by mass. The kneaded product of (C1) and the metal compound (E) is contained in an amount of 1 to 99 parts by mass, and the non-crosslinked olefin resin (B) is contained in an amount of 1 to 99 parts by mass. The thermoplastic elastomer composition according to claim 1. An ethylene / α-olefin / nonconjugated polyene copolymer rubber obtained from ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene, wherein the olefin rubber (A) at least partially crosslinked is; Obtained by crosslinking at least one olefinic rubber (A1) selected from ethylene and α-olefin copolymer rubber obtained from ethylene and an α-olefin having 3 to 20 carbon atoms,
The non-crosslinked olefin resin (B) is at least one olefin resin selected from a propylene homopolymer, a propylene copolymer, and an ethylene copolymer. The thermoplastic elastomer composition as described.   The softener (H) further includes an olefin rubber (A) that is at least partially crosslinked, an uncrosslinked olefin resin (B), and an olefin resin having a functional group. It is contained in an amount of 1 to 200 parts by mass with respect to a total of 100 parts by mass of (C1) and the kneaded product of the metal compound (E). The thermoplastic elastomer composition as described.   An olefinic resin further comprising a fluororesin (J), wherein the fluororesin (J) is at least partially crosslinked olefinic rubber (A), non-crosslinked olefinic resin (B), and functional group It is contained in an amount of 0.05 to 20 parts by mass with respect to a total of 100 parts by mass of (C1) and the kneaded product of the metal compound (E). The thermoplastic elastomer composition according to Item. In the presence of a crosslinking agent (D) for crosslinking the olefin rubber (A1), the olefin rubber (A1) and the non-crosslinked olefin resin (B) are dynamically heat-treated to obtain an olefin rubber (A1). ) Is at least partially crosslinked olefin rubber (A),
A step [I] of producing a dynamically heat-treated product containing at least a partially crosslinked olefinic rubber (A) and a non-crosslinked olefinic resin (B);
Kneading the dynamically heat-treated product obtained in step [I], the olefin resin (C1) having a functional group, and the metal compound (E) capable of reacting with the functional group of the olefin resin (C1),
Heat containing an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), and a kneaded product of the olefin resin (C1) having a functional group and the metal compound (E) A plastic elastomer composition comprising:
The olefin resin (C1) having a functional group is at least one olefin resin selected from maleic acid-modified propylene homopolymer, maleic acid-modified propylene copolymer, and maleic acid-modified ethylene copolymer. ,
The thermoplastic elastomer composition has a sea-island structure, and an island phase containing an olefinic rubber (A) comprises a kneaded product of an olefinic resin (C1) and a metal compound (E), and a non-crosslinked olefinic resin ( A thermoplastic elastomer composition obtained from the step [II] of producing a thermoplastic elastomer composition dispersed in a sea phase containing B). In the presence of a crosslinking agent (D) for crosslinking the olefin rubber (A1), the olefin rubber (A1) and the non-crosslinked olefin resin (B) are dynamically heat-treated to obtain an olefin rubber (A1). ) Is at least partially crosslinked olefin rubber (A),
A step [I] of producing a dynamically heat-treated product containing at least a partially crosslinked olefinic rubber (A) and a non-crosslinked olefinic resin (B);
Kneading the dynamically heat-treated product obtained in step [I], the olefin resin (C1) having a functional group, and the metal compound (E) capable of reacting with the functional group of the olefin resin (C1),
Heat containing an olefin rubber (A) that is at least partially crosslinked, a non-crosslinked olefin resin (B), and a kneaded product of the olefin resin (C1) having a functional group and the metal compound (E) A plastic elastomer composition comprising:
The olefin resin (C1) having a functional group is at least one olefin resin selected from maleic acid-modified propylene homopolymer, maleic acid-modified propylene copolymer, and maleic acid-modified ethylene copolymer. ,
The thermoplastic elastomer composition has a sea-island structure, and an island phase containing an olefinic rubber (A) comprises a kneaded product of an olefinic resin (C1) and a metal compound (E), and a non-crosslinked olefinic resin ( And a step [II] of producing a thermoplastic elastomer composition dispersed in a sea phase containing B). A molded article comprising the thermoplastic elastomer composition according to any one of claims 1 to 6 . A thermoplastic elastomer composition for foaming, comprising the thermoplastic elastomer composition according to any one of claims 1 to 6 and a foaming agent (K). The foaming thermoplastic elastomer composition according to claim 9 , wherein the foaming agent (K) is 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 according to claim 9 or 10 , wherein the foaming agent (K) is an inorganic or organic pyrolytic chemical foaming agent or a physical foaming agent. A molded article obtained from the thermoplastic elastomer composition for foaming according to any one of claims 9 to 11 . A foam obtained from the thermoplastic elastomer composition for foaming according to any one of claims 9 to 11 . An automobile part comprising the foam according to claim 13 . A building material comprising the foam according to claim 13 .

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