JP2013159635A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition including a hydrogenated styrene thermoplastic elastomer and hardly exhibiting dynamic anisotropy during molding.SOLUTION: A thermoplastic elastomer composition includes: a hydrogenated styrene thermoplastic elastomer; and a copolymer of a conjugated diene compound and a nonconjugated olefin. The hydrogenated styrene thermoplastic elastomer is at least one of a styrene-ethylene/butylene-styrene triblock copolymer and a styrene-ethylene/propylene-styrene triblock copolymer.

Description

  The present invention relates to a thermoplastic elastomer composition which contains a hydrogenated styrene thermoplastic elastomer and hardly exhibits mechanical anisotropy during molding.

Styrenic thermoplastic elastomers are widely used in asphalt additives (Patent Document 1), resin additives, shoe soles (Patent Documents 2 and 3), and the like.
As the styrenic thermoplastic elastomer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / butylene- Examples thereof include a styrene triblock copolymer (SEBS) and a styrene-ethylene / propylene-styrene triblock copolymer (SEPS). Here, SEBS is a hydrogenated SBS soft segment (polybutadiene part), and SEPS is a hydrogenated SIS soft segment (polyisoprene part).
In these styrenic thermoplastic elastomers, a hard segment composed of a styrene block constitutes a physical crosslinking point, a soft segment exhibits rubber elasticity, and the rubber elasticity as a whole develops rubber elasticity.

These styrenic thermoplastic elastomers may exhibit mechanical anisotropy during molding due to differences in compatibility between soft segments and hard segments, differences in flow characteristics during melting, and the like (for example, Patent Document 4). ). In particular, hydrogenated styrene-based thermoplastic elastomers such as SEBS and SEPS tend to exhibit mechanical anisotropy at the time of molding as compared with SBS and SIS having the same styrene content.
In addition, in patent document 4, when manufacturing the fluid transport tube which consists of a thermoplastic elastomer or a composition containing the same, it implements the tension | tensile_strength process pulled until the maximum tension rate becomes 30% or more in an extrusion direction after extrusion molding. Thus, the mechanical anisotropy of the tube is suppressed.

Japanese Patent Laid-Open No. 10-017777 JP 10-1114850 A Kaihei 10-168235 Japanese Patent Laid-Open No. 2008-020054

As in Patent Document 4, since it is cumbersome to carry out a tensioning step after molding, it is desirable that the composition itself containing a thermoplastic elastomer hardly causes mechanical anisotropy. In particular, a hydrogenated styrene-based thermoplastic elastomer is more susceptible to mechanical anisotropy than a non-hydrogenated styrene-based thermoplastic elastomer, and therefore, a hydrogenated styrene-based thermoplastic elastomer-containing composition that hardly generates mechanical anisotropy. Is desired.
An object of the present invention is to provide a thermoplastic elastomer composition that contains a hydrogenated styrene-based thermoplastic elastomer and hardly exhibits mechanical anisotropy during molding.

The present inventor has found that the problem of the present invention can be solved by blending a specific copolymer with a hydrogenated styrene-based thermoplastic elastomer, and has completed the present invention.
That is, the present invention is a thermoplastic elastomer composition comprising a hydrogenated styrene-based thermoplastic elastomer and a copolymer of a conjugated diene compound and a nonconjugated olefin.

  According to the present invention, it is possible to provide a thermoplastic elastomer composition that is less likely to exhibit mechanical anisotropy during molding than a hydrogenated styrene thermoplastic elastomer.

The thermoplastic elastomer composition according to the present invention comprises a hydrogenated styrene thermoplastic elastomer, and a copolymer of a conjugated diene compound and a nonconjugated olefin.
Thus, the expression of the mechanical anisotropy at the time of shaping | molding can be suppressed by mix | blending the said copolymer with a hydrogenated styrene-type thermoplastic elastomer. The reason for this is not clear, but when a hydrogenated styrene thermoplastic elastomer is molded, it is thought that mechanical anisotropy occurs due to the hydrogenated styrene thermoplastic elastomer being aligned in a certain direction due to stress applied during molding. It is presumed that this anisotropy is alleviated when the copolymer is added to the hydrogenated styrene thermoplastic elastomer.

<Hydrogenated styrene thermoplastic elastomer>
Next, the hydrogenated styrenic thermoplastic elastomer contained in the thermoplastic elastomer composition according to the present invention will be described.
The hydrogenated styrene-based thermoplastic elastomer used in the present invention is a hydrogenated product of a styrene-based thermoplastic elastomer (that is, a block copolymer using polystyrene as a hard segment in a molecule and polydiene such as polybutadiene or isoprene as a soft segment). The styrene-ethylene / butylene-styrene triblock copolymer (SEBS), the styrene-ethylene / propylene-styrene triblock copolymer (SEPS), and the random type styrene-butadiene rubber A hydrogenated polymer (HSBR) etc. are mentioned. In the present invention, these hydrogenated styrene thermoplastic elastomers can be used alone or in combination of two or more.

  The content of the styrene block in the hydrogenated styrene-based thermoplastic elastomer is from the viewpoint of isotropy during molding, mechanical strength, heat stability, weather resistance, chemical resistance, gas barrier properties, flexibility, workability, etc. It is 60-10 mass%, More preferably, it is 50-20 mass%, More preferably, it is 40-25 mass%.

The weight average molecular weight (Mw) of the hydrogenated styrenic thermoplastic elastomer is preferably 1,000,000 or less, more preferably 750,000 or less, and even more preferably 50, from the viewpoint of improving fracture behavior without impairing processability. 10,000 or less.
Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. When the molecular weight distribution is 10 or less, physical properties (mechanical strength, heat stability, weather resistance, chemical resistance, gas barrier properties, flexibility, workability, moldability, etc.) are uniform.

  Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The melt flow rate (MFR; ASTM D 1238, 230 ° C., load: 2.16 kg) of the hydrogenated styrenic thermoplastic elastomer is preferably 0.1 to 100 g / 10 minutes, more preferably 0.3 to 60 g. / 10 minutes. Within this range, the handleability will be good.
The solubility parameter δ (SP value) of the hydrogenated styrenic thermoplastic elastomer is preferably in the range of 7 to 9 (cal · cc ⁻¹ ) ^1/2 .
When the solubility parameter δ (SP value) of the hydrogenated styrene-based thermoplastic elastomer is within this range, the compatibility with the copolymer (a copolymer of a conjugated diene compound and a non-conjugated olefin) is improved. The impact resistance and fracture characteristics of the resin composition can be improved.

The solubility parameter δ (cal · cc ⁻¹ ) ^1/2 is defined by the following formula (1) in consideration of the attractive force between molecules in the Hildebrand-Scatchard solution theory.
δ = (ΔE _V / V ₁ ) ^1/2 (1)
Here, ΔE _V represents evaporation energy, V ₁ represents molecular volume, and ΔE _V / V ₁ represents cohesive energy density (CED).
The solubility parameter δ (SP value) in the present invention is a value calculated according to the Fedors method.

<Copolymer of conjugated diene compound and non-conjugated olefin>
Next, a copolymer of a conjugated diene compound and a non-conjugated olefin will be described.
≪Constitution of copolymer of conjugated diene compound and non-conjugated olefin≫
The cis-1,4-bond amount of the conjugated diene compound-derived portion (conjugated diene portion) of the copolymer of a conjugated diene compound and a non-conjugated olefin used in the present invention is preferably 50% or more, more preferably It is over 92%, more preferably 95% or more. If the amount of cis-1,4 bonds in the conjugated diene compound portion (part derived from the conjugated diene compound) is 50% or more, a low glass transition point (Tg) can be maintained, and thereby, impact resistance at low temperatures can be maintained. Improved.
By making the cis-1,4-bond content of the conjugated diene compound-derived moiety (conjugated diene moiety) greater than 92%, it is possible to improve impact resistance, crack growth resistance, weather resistance, and heat resistance at low temperatures. It becomes. Further, when the cis-1,4-bond amount of the conjugated diene compound-derived portion (conjugated diene portion) is 95% or more, impact resistance, crack growth resistance, weather resistance, and heat resistance at low temperatures can be further improved. .
The amount of cis-1,4 bonds is the amount in the conjugated diene compound-derived moiety, and is not a ratio relative to the entire copolymer.

  The proportion of the non-conjugated olefin-derived portion in the copolymer of the conjugated diene compound and the non-conjugated olefin is preferably 10 to 70 mol%. Within this range, the impact resistance is good. From this viewpoint, the proportion of the non-conjugated olefin-derived portion in the copolymer is more preferably 20 to 70 mol%, still more preferably 20 to 50 mol%, and still more preferably 20 to 35 mol%.

  The non-conjugated olefin is preferably an acyclic olefin. Moreover, it is preferable that carbon number of a nonconjugated olefin is a 2-10 alpha olefin. Since the α-olefin has a double bond at the α-position of the olefin, it can be efficiently copolymerized with the conjugated diene compound. Accordingly, preferred examples of non-conjugated olefins include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and among these, ethylene, propylene and 1-butene is preferred and ethylene is more preferred. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  The conjugated diene compound preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  The copolymer used in the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  The copolymer of the conjugated diene compound and the non-conjugated olefin does not cause a problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a polymer structural material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer of the conjugated diene compound and the nonconjugated olefin is preferably 10,000 to 10,000,000. 1,000,000 is more preferable, and 50,000-600,000 is still more preferable. If the Mw is 10,000,000 or less, the moldability is good.

The copolymer used in the present invention preferably has a conjugated diene compound-derived portion having a content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound of 5% or less. More preferably, it is 3% or less, More preferably, it is 2.5% or less.
When the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is 5% or less, the copolymer used in the present invention has weather resistance and ozone resistance. The property can be further improved. Furthermore, when the 1,2-adduct (including 3,4-adduct) content of the conjugated diene compound portion is 2.5% or less, the copolymer further improves ozone resistance and fatigue resistance. Can do.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. If the molecular weight distribution is 10 or less, the physical properties are uniform.
Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The copolymer of the conjugated diene compound and the non-conjugated olefin used in the present invention may be a random copolymer or a block copolymer. Alternatively, a taper copolymer may be used. The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, from a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. And at least one block portion (also referred to as a block structure) and a random portion (also referred to as a random structure) in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. It is a copolymer.
That is, the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously.
Alternatively, it may be an alternating copolymer in which conjugated diene compounds and non-conjugated olefins are alternately arranged (a molecular chain structure of -ABABABAB-, where A is a conjugated diene compound and B is a non-conjugated olefin). .

The structure of the block copolymer is (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of monomer units of a conjugated diene compound). And B is a block portion composed of monomer units of non-conjugated olefin, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multiblock copolymer.

  In the case of the block copolymer, the block portion composed of the monomer unit of the non-conjugated olefin exhibits static crystallinity, and thus is excellent in mechanical properties such as breaking strength and gas barrier properties.

  When the copolymer of the conjugated diene compound and the non-conjugated olefin is a random copolymer, since the arrangement of the monomer units of the non-conjugated olefin is irregular, the copolymer does not cause phase separation, The crystallization temperature derived from the block part is not observed. That is, the heat resistance of the copolymer is improved. This makes it possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer.

  It is preferable that content of the said copolymer (copolymer of a conjugated diene compound and a nonconjugated olefin) is 1-110 mass parts with respect to 100 mass parts of the above-mentioned hydrogenated styrene-type thermoplastic elastomer. By setting it within this range, mechanical anisotropy during molding can be satisfactorily suppressed. From this viewpoint, the content of the copolymer is more preferably 1 to 100 parts by mass, still more preferably 50 to 100 parts by mass, and still more preferably 70 to 100 parts by mass.

≪Method for producing copolymer of conjugated diene compound and non-conjugated olefin≫
Next, the manufacturing method of a copolymer is demonstrated in detail. However, the manufacturing method described in detail below is merely an example. The copolymer used in the present invention can be produced by polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  A method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin includes, for example, (1) a polymerization catalyst composition in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The components of the product may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

  Moreover, in the manufacturing method of the copolymer of a conjugated diene compound and a nonconjugated olefin, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  The polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 to 200 ° C., for example, and may be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.

  In the polymerization of the conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound, the pressure of the non-conjugated olefin is preferably 0.1 to 10 MPa. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Moreover, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches a peak, and therefore the pressure of the non-conjugated olefin is preferably 10 MPa or less.

  In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) preferably satisfies the relationship of the following formula. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7

  According to the above production method, except that the polymerization catalyst or the polymerization catalyst composition is used, the monomer conjugated diene compound and the non-conjugated compound are produced in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst. Olefin can be copolymerized. In addition, the more specific manufacturing method of the copolymer of the said conjugated diene compound and nonconjugated olefin used by this invention is as having described in WO2011 / 016210, for example.

<Other ingredients>
-Filler The thermoplastic elastomer composition according to the present invention may contain a filler. As the filler, those generally used without particular limitation can be used as necessary.
Specific examples of inorganic fillers include silicates such as fine powder talc, kaolinite, calcined clay, biophylite, sericite, and wollastonite, carbonates such as precipitated calcium carbonate, heavy calcium carbonate, and magnesium carbonate. Powders such as hydrous aluminum, magnesium hydroxide and other hydroxides, zinc oxide, zinc oxide, magnesium oxide and other oxides, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and anhydrous silicic acid Flaky filler such as mica; fibrous filler such as basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotlite, potassium titanate, elestite Glass balun, fly ashba Balun fillers such emissions; and the like.

-Rubber component You may mix | blend another rubber component and another resin component with the thermoplastic-elastomer composition which concerns on this invention. Other rubber components are not particularly limited and may be appropriately selected depending on the purpose. For example, other conjugated diene compounds and copolymers of nonconjugated olefins, natural rubber, various butadiene rubbers, various styrene- Butadiene copolymer rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene Copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine Rubber, urethane rubber Etc., and the like. These may be used individually by 1 type and may use 2 or more types together.

Additives The thermoplastic elastomer composition of the present invention includes softeners, nucleating agents, antioxidants, anti-aging agents, hydrochloric acid absorbents, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents. Agent, flame retardant, pigment, dye, dispersant, copper damage inhibitor, neutralizing agent, foaming agent, plasticizer, anti-bubble agent, cross-linking agent, cross-linking aid, cross-linking accelerator, peroxide, etc. Additives such as an agent, a heweld strength improver, a plasticizer, a processing aid, a weathering stabilizer, an anti-coloring agent, and an anti-blooming agent may be included.
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, and a sulfur compound. System crosslinking agent, oxime-nitrosamine system crosslinking agent sulfur and the like.

<Manufacture of thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention is obtained by mixing the above-mentioned various components and melting and kneading the hydrogenated styrene-based thermoplastic elastomer and a copolymer (a copolymer of a conjugated diene compound and a non-conjugated olefin). Can be manufactured. From the viewpoint of sufficient melting and kneading while saving time and energy, the melting and kneading temperature is preferably 100 to 250 ° C, more preferably 120 to 230 ° C.
This thermoplastic elastomer composition is suitably used for a tube such as a liquid transport tube or a movable cable tube.
Moreover, the molding method applied with respect to the conventional resin composition is applicable to this thermoplastic elastomer composition without a restriction | limiting in particular. As the molding method, a known molding method such as injection molding, extrusion molding, vacuum / pressure molding or the like can be employed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The analysis method of ethylene-butadiene copolymer (EBR) and the evaluation method of a thermoplastic elastomer composition are shown below.

<Analytical method of ethylene-butadiene copolymer (EBR (a) and EBR (b))>
・ Copolymer microstructure (1,2-vinyl bond content, cis-1,4 bond content)
The microstructure of the butadiene moiety in the copolymer (1,2-vinyl bond content) was determined from the 1,2-vinyl bond component (5.0 by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm)). -5.1 ppm) and the integral ratio of the entire butadiene bond component (5-5.6 ppm). Further, the microstructure (cis-1,4 bond amount) of the butadiene moiety in the copolymer is determined based on the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). (26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm) were obtained from the integral ratio.

-Ethylene content of copolymer The content (mol%) of the ethylene moiety in the copolymer is the total ethylene bond component (28 according to ¹³ C-NMR spectrum (100 ° C, d-tetrachloroethane standard: 73.8 ppm). .5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm).

-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.

-Block polyethylene melting point of copolymer (DSC peak temperature)
Differential scanning calorimetry (DSC) was performed according to JIS K7121-1987, a DSC curve was drawn, and a block polyethylene melting point (DSC peak temperature) was measured. In order to avoid the influence of impurities such as single polymer and catalyst residue, the measurement is performed by immersing the copolymer in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then using the dried rubber component as a sample. did.

-Identification of copolymer The chain distribution was analyzed by applying the ozonolysis-GPC method in the literature ("Proceedings of the Society of Polymer Science, Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.].

<Evaluation method>
-Tensile strength and elongation From each sheet obtained in the examples and comparative examples, a dumbbell-shaped No. 3 type (JIS K6251) first sample extending in the direction parallel to the sheet extrusion direction and extending in the orthogonal direction. An existing dumbbell-shaped No. 3 second sample was cut out and prepared. For these first and second samples, the tensile strength and elongation were measured at 23 ° C. according to JIS K6251.
Next, anisotropy (tensile strength) and anisotropy (elongation) were calculated according to the following formula.
Anisotropy (tensile strength) = tensile strength (second sample) / tensile strength (first sample)
Anisotropy (elongation) = elongation (second sample) / elongation (first sample)
-Rigidity The tube was bent at a bending radius of 10 mm and evaluated by the presence or absence of kinks. Evaluation was performed according to the following criteria. The measurement results are shown in Table 1.
OK: No kink is generated. NG: Kink is generated.

Production Example 1
((A) Production of block polymerization type of ethylene-butadiene copolymer (EBR))
After adding 150 ml of toluene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 14.5 μmol was placed in a glass container. , Triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 14.1 μmol and diisobutylaluminum hydride 0.87 mmol were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 14.1 μmol in terms of gadolinium was added to the monomer solution, and polymerization was carried out at 50 ° C. for 5 minutes. Thereafter, 20 ml of a toluene solution containing 3.05 g (0.056 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 15 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was reduced at a rate of 0.2 MPa / min, while 6.09 g (0. The operation of adding 40 ml of a toluene solution containing 113 mol) and then performing polymerization for another 30 minutes was repeated a total of 3 times. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol. And vacuum-dried at 70 ° C. to obtain a polymer. The yield of the obtained copolymer (a) was 24.50 g.
For the obtained copolymer (a), the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), block polyethylene melting point (DSC peak temperature) and chain structure were measured by the above methods. ·evaluated.
As the microstructure of the butadiene portion in the copolymer (a), the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.4%.
The weight average molecular weight Mw was 205,000, and the molecular weight distribution Mw / Mn was 9.15.
The ethylene content was 34 mol%.
The block polyethylene melting point (DSC peak temperature) was 121 ° C., and the chain structure was a block.

Production Example 2
((B) Production of random polymerization type of ethylene-butadiene copolymer (EBR))
After adding 700 ml of a toluene solution containing 28.0 g (0.52 mol) of 1,3-butadiene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, dimethylaluminum (μ-dimethyl) bis (2-phenylindenyl) neodymium [(2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe _{2 is} placed in a glass container in a glove box under a nitrogen atmosphere. 400.0 μmol and 200.0 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) were charged and dissolved in 80 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 390.0 μmol in terms of neodymium was added to the monomer solution, and polymerization was performed at room temperature for 120 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a copolymer (b). The yield of the obtained copolymer (b) was 18.00 g.
About the obtained copolymer (b), the microstructure, ethylene content rate, the weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured and evaluated by said method.
As the microstructure of the butadiene portion in the copolymer (b), the cis-1,4-bond amount was 91% and the 1,2-vinyl bond amount was 2.1%.
The weight average molecular weight Mw was 263,000, and the molecular weight distribution Mw / Mn was 1.58. The ethylene content was 15 mol%.
Since the chain structure of the ethylene-butadiene copolymer (EBR) (b) is random, the ethylene part of the copolymer (b) having a random structure is taken out, and the taken-out ethylene part is taken as the copolymer (b The melting temperature of the hypothetical polymer obtained by homopolymerization under the same conditions as in the synthesis of ()) was taken as the melting temperature of the ethylene portion of the random copolymer.
The melting temperature of the ethylene part of the copolymer (b) was 110 ° C.

Examples 1-4 and Comparative Examples 1-3
According to the blending contents shown in Table 1, a thermoplastic elastomer composition was prepared by kneading at 200 ° C. and 150 rpm using a twin screw extruder and pelletizing with a pelletizer.
Next, using the pellets of the obtained examples and comparative examples, under manufacturing conditions of a mold temperature of 80 ° C. and a resin temperature of 200 ° C., an inner diameter of 1.0 mm, a thickness of 0.5 mm, a length of 100 mm, and an outer diameter of 2 mm The tube was prepared by a hot press method, and a sheet having a thickness of 0.5 mm × 100 mm × 100 mm was produced by extrusion molding.
Tensile strength and elongation were measured using a sheet, and rigidity was measured using a tube. The results are shown in Table 1.

In addition, as a component shown in Table 1, the following were used.
SEPS: styrene-ethylene / propylene-styrene triblock copolymer,
Product name “Septon S2006”, manufactured by Kuraray Co., Ltd.
Styrene partial content 35mol%
-BR: Butadiene rubber, manufactured by JSR Corporation, trade name "JSR BR01",
Mw 550000

  As is clear from Table 1, the thermoplastic elastomer compositions of the examples have smaller anisotropy (tensile strength) and anisotropy (elongation) and rigidity than the thermoplastic elastomer compositions of the comparative examples. It was found to be good.

Examples 5-8 and Comparative Examples 4-6
According to the blending contents shown in Table 2, a thermoplastic elastomer composition was prepared by kneading at 200 ° C. and 150 rpm using a twin screw extruder and pelletizing with a pelletizer.
Next, using the pellets of the obtained examples and comparative examples, under manufacturing conditions of a mold temperature of 80 ° C. and a resin temperature of 200 ° C., an inner diameter of 1.0 mm, a thickness of 0.5 mm, a length of 100 mm, and an outer diameter of 2 mm The tube was prepared by a hot press method, and a sheet having a thickness of 0.5 mm × 100 mm × 100 mm was produced by extrusion molding.
Tensile strength and elongation were measured using a sheet, and rigidity was measured using a tube. The results are shown in Table 2.

In addition, as a component shown in Table 2, the following were used.
SEPS: styrene-ethylene / butylene-styrene triblock copolymer,
Product name "Septon S8006", manufactured by Kuraray Co., Ltd.
Styrene partial content 34 mol%
-BR: Butadiene rubber, manufactured by JSR Corporation, trade name "JSR BR01",
Mw 550000

  As is clear from Table 2, it was found that the examples had smaller anisotropy (tensile strength) and anisotropy (elongation) and better rigidity than the comparative examples.

Claims (14)

A hydrogenated styrene-based thermoplastic elastomer;
A thermoplastic elastomer composition comprising a conjugated diene compound and a copolymer of a non-conjugated olefin.   The thermoplastic elastomer composition according to claim 1, wherein the content of the copolymer is 1 to 100 parts by mass with respect to 100 parts by mass of the hydrogenated styrene-based thermoplastic elastomer.   The heat according to claim 1 or 2, wherein the hydrogenated styrenic thermoplastic elastomer is at least one of a styrene-ethylene / butylene-styrene triblock copolymer and a styrene-ethylene / propylene-styrene triblock copolymer. Plastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein a cis-1,4 bond amount of a conjugated diene compound portion of the copolymer is 50% or more.   The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein in the copolymer, the proportion of the non-conjugated olefin-derived portion is 20 mol% to 70 mol%.   The thermoplastic elastomer composition according to claim 1, wherein the copolymer is a block copolymer.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the copolymer has a weight average molecular weight in terms of polystyrene of 10,000 to 10,000,000.   The thermoplastic elastomer composition according to any one of claims 1 to 7, wherein a molecular weight distribution (Mw / Mn) of the copolymer is 10 or less.   The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the non-conjugated olefin is an acyclic olefin.   The thermoplastic elastomer composition according to any one of claims 1 to 9, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The thermoplastic elastomer composition according to claim 9, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The thermoplastic elastomer composition according to claim 11, wherein the non-conjugated olefin is ethylene.   The thermoplastic elastomer composition according to any one of claims 1 to 12, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The thermoplastic elastomer composition according to any one of claims 1 to 13, wherein the hydrogenated styrene-based thermoplastic elastomer has a solubility parameter value of 7 to 9.