JP2017132920A - Thermoplastic polymer composition for damping material, manufacturing method of molded body and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition for damping material capable of enhancing tanδ at 23°C.SOLUTION: The thermoplastic polymer composition for damping material contains a 4-methyl-1-pentene α-olefin copolymer (A) containing a constitutional unit (A-i) derived from 4-methyl-1-pentene and a constitutional unit (A-ii) derived from other α-olefin with the constitutional unit (A-i) of 63 to 86 mol% and the constitutional unit (A-ii) of 14 to 37 mol% and a thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing a copolymer [B-I] containing a constitutional unit (B-i) derived from ethylene, a constitutional unit (B-ii) derived from other α-olefin and a constitutional unit (B-iii) derived from non-conjugated polyene and a polyolefin resin [B-II] and has mass ratio of the copolymer (A) and the composition (B), (A)/(B), of 10/90 to 49/51.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic polymer composition for damping material, a method for producing a molded body, and a molded body.

  Parts and housings for personal computers, OA equipment, AV equipment, mobile phones, optical equipment, precision equipment, electrical and electronic equipment including home and office electrical appliances, and toys, and railway vehicles, automobiles, ships and aircraft In addition to general material properties including impact resistance, heat resistance, strength, and dimensional stability, molded bodies used in industrial fields and parts such as building materials are required to have vibration damping properties. Therefore, a damping material is used for such a molded body.

  The damping property required for the damping material can be evaluated by, for example, a loss tangent tan δ that is a ratio (G ″ / G ′) of the storage elastic modulus (G ′) and the loss elastic modulus (G ″). For this reason, the higher the tan δ in the temperature environment in which the damping material is used, the stronger the viscosity is exhibited. Therefore, it is easier to absorb the stress caused by vibration, and higher damping properties are exhibited. Note that tan δ varies depending on the temperature. Therefore, the maximum value of tan δ of the damping material (hereinafter also referred to as “tan δ peak value”) and the temperature at which the value of tan δ becomes maximum (hereinafter also simply referred to as “tan δ peak temperature”) are adjusted to a specific range. Technology has been developed.

  For example, Patent Document 1 discloses a shock absorber composition containing a copolymer containing a vinyl aromatic compound such as styrene, and a tan δ peak obtained by dynamic viscoelasticity measurement (1 Hz) of the copolymer. The temperature is in the range of more than 0 ° C. and not more than 20 ° C., and the tan δ value is 0.4 or more in the entire temperature range from 5 ° C. to 15 ° C., and the tan δ value at 15 ° C. is 0.5 or more. An impact absorber composition is disclosed.

No. 2008/102761

  A composition containing a copolymer containing styrene as in Patent Document 1 tends to have a low tan δ peak temperature, and at room temperature (for example, 23 ° C.), the value of tan δ is small, so that sufficient vibration damping properties cannot be obtained. There was a thing.

  In view of the above problems, the present invention is capable of further increasing tan δ at 23 ° C., a thermoplastic polymer composition for vibration damping materials, and a method for producing a molded body using such a thermoplastic polymer composition. And an object of the present invention is to provide a molded article formed from such a thermoplastic polymer composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a resin composition having a specific composition, and have completed the present invention.

That is, the present invention relates to the following [1] to [15].
[1] At least one α- selected from a structural unit derived from 4-methyl-1-pentene (Ai) and an α-olefin having 2 to 20 carbon atoms excluding 4-methyl-1-pentene A 4-methyl-1-pentene / α-olefin copolymer containing a structural unit derived from an olefin (A-ii) and optionally containing a structural unit derived from a non-conjugated polyene (A-iii) , When the total of the structural units (A-i), (A-ii) and (A-iii) is 100 mol%, the structural unit (A-i) is 63 to 86 mol%, the structural unit (A- 4-methyl-1-pentene / α-olefin copolymer (A) containing 14 to 37 mol% of ii) and 0 to 10 mol% of the structural unit (A-iii);
A copolymer comprising a structural unit derived from ethylene (B-i), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (B-ii), and a structural unit derived from a non-conjugated polyene (B-iii). A thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing a polymer [BI] and a polyolefin resin [B-II],
The mass ratio (A) / (B) of the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B) is 10/90 to 49/51. A thermoplastic polymer composition for a vibration damping material.
[2] In the 4-methyl-1-pentene / α-olefin copolymer (A), the total of the structural units (Ai), (A-ii) and (A-iii) is 100 mol%. 3 to 63% of the structural unit (A-i), 20 to 37% by mole of the structural unit (A-ii), and 0 to 10% by mole of the structural unit (A-iii). The thermoplastic polymer composition for a vibration damping material according to [1], which is a methyl-1-pentene / α-olefin copolymer.
[3] The 4-methyl-1-pentene / α-olefin copolymer (A) is a copolymer in which a melting point is not observed or a melting point is less than 135 ° C. [1] Or the thermoplastic polymer composition for damping materials as described in [2].
[4] The 4-methyl-1-pentene / α-olefin copolymer (A) is characterized in that the melting point is not observed or the copolymer is less than 110 ° C. 3] The thermoplastic polymer composition for a vibration damping material according to any one of the above.
[5] The heat for a damping material according to any one of [1] to [4], wherein the temperature at which the value of the loss tangent tan δ is maximum is a copolymer having a temperature of 0 ° C. to 40 ° C. Plastic polymer composition.
[6] A method for producing a molded body, comprising a step of molding the thermoplastic polymer composition for a vibration damping material according to any one of [1] to [5].
[7] The manufacturing method according to [6], wherein the molded body is a vibration damping member.
[8] The manufacturing method according to [6], wherein the molded body is an impact absorbing material.
[9] The manufacturing method according to [6], wherein the molded body is a vibration absorbing material.
[10] The manufacturing method according to [6], wherein the molded body is a resonance absorber.
[11] A molded article comprising the thermoplastic polymer composition for a vibration damping material according to any one of [1] to [5].
[12] The molded article according to [11], which is a vibration damping member.
[13] The molded article according to [11], which is an impact absorbing material.
[14] The molded article according to [11], which is a vibration absorbing material.
[15] The molded article according to [11], which is a resonance absorber.

  According to the present invention, a thermoplastic polymer composition for a vibration damping material that can further increase tan δ at 23 ° C., a method for producing a molded body using such a thermoplastic polymer composition, and such A molded body is provided that is molded from a novel thermoplastic polymer composition.

  Hereinafter, the thermoplastic polymer composition for a vibration damping material of the present invention and a method for producing a molded product obtained therefrom will be described in detail. The molded product obtained by the production method of the present invention includes various vibration damping materials.

1. Thermoplastic polymer composition for damping material The thermoplastic polymer composition for damping material of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is 4-methyl-1-pentene / α-. An olefin copolymer (A) (hereinafter also simply referred to as “copolymer (A)”) and a thermoplastic elastomer composition (B) (hereinafter also simply referred to as “composition (B)”). contains.

  The composition of the present invention may contain only one type of copolymer (A) or two or more types of copolymers (A). Moreover, the composition of this invention may contain only 1 type of compositions (B), and may contain 2 or more types of compositions (B).

  The composition of the present invention may contain components other than the copolymer (A) and the composition (B) as long as the effects of the present invention are exhibited.

  The mass ratio of the copolymer (A) and the composition (B) contained in the composition of the present invention (the mass of the copolymer (A) / the mass of the composition (B), hereinafter simply “(A ) / (B) ”) is 10/90 to 49/51. From the viewpoint of more suitably achieving the effects of the present invention, (A) / (B) is preferably 10/90 to 45/55, more preferably 15/85 to 45/55, More preferably, it is 30/85 to 45/55.

  The composition of the present invention has a tan δ peak value of 0.1 or more and 3.0 or less obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. It is preferable that it is 0.2 or more and 3.0 or less, and it is more preferable that it is 0.25 or more and 3.0 or less.

  The composition of the present invention has a tan δ peak temperature of the copolymer (A) obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. It is preferably 10 ° C or higher and 40 ° C or lower, more preferably 15 ° C or higher and 40 ° C or lower, and further preferably 15 ° C or higher and 30 ° C or lower.

According to JIS K6253, the composition of the present invention is measured in the state of a press sheet having a thickness of 3 mm, and the Shore A hardness value immediately after the start of pressing needle contact and the Shore A after 15 seconds from the start of pressing needle contact. The change amount ΔHS between the hardness values is preferably 5 or more, 50 or less, more preferably 5 or more and 45 or less, and still more preferably 10 or more and 45 or less.
Note that ΔHS is a value obtained according to the following equation.
ΔHS = (Shore A hardness value immediately after start of pressing needle contact−Shore A hardness value 15 seconds after start of pressing needle contact)

The composition of the present invention preferably has a Lupke rebound elastic modulus measured according to JIS K6255 of 50 or less, more preferably 45 or less, and even more preferably 40 or less.
Note that ΔHS is a value obtained according to the following equation.

  Hereinafter, each component and each requirement will be described.

  In addition, the composition and physical properties of the copolymer (A) and the composition (B) constituting the composition of the present invention are separated by a conventionally known method, and each component is described in the following method or conventionally known. Can be measured by the method.

1-1. Copolymer (A)
The copolymer (A) includes a structural unit (Ai) derived from 4-methyl-1-pentene (hereinafter, also simply referred to as “structural unit (Ai)”), and 4-methyl-1- Structural unit (A-ii) derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding pentene (hereinafter also simply referred to as “structural unit (A-ii)”). ) And optionally a structural unit (A-iii) derived from a non-conjugated polyene (hereinafter also simply referred to as “structural unit (A-iii)”)) 4-methyl-1-pentene / α- It is an olefin copolymer. As long as the effect of the present invention is exhibited, the copolymer (A) may contain a structural unit other than the above (hereinafter also simply referred to as “other structural unit”).

  The copolymer (A) is composed of 63 mol% or more of the structural unit (Ai) when the total of the structural units (Ai), (A-ii), and (A-iii) is 100 mol%. 86 mol% or less, 14 mol% or more and 37 mol% or less of the structural unit (A-ii), and 0 mol% or more and 10 mol% or less of the structural unit (A-iii). Since the copolymer (A) contains 63 mol% or more and 86 mol% or less of the structural unit (Ai), the molded product obtained by molding the composition of the present invention has a stress relaxation property at room temperature ( It is possible to improve the shape following property such as unevenness, and to improve the stress absorbability (tan δ) at room temperature. The above viewpoint is that when the total of the structural units (A-i), (A-ii) and (A-iii) is 100 mol%, the structural unit (A-i) is 63 mol% or more and 80 mol% or less. The structural unit (A-ii) is preferably contained in an amount of 20 mol% to 37 mol% and the structural unit (A-iii) is preferably contained in an amount of 0 mol% to 10 mol%.

  Examples of the structural unit (A-ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-octene, Structural units derived from decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene and 1-eicocene are included. Among these, the ease of polymerization when producing the copolymer (A) is increased, and the flexibility, stress relaxation at room temperature, and stress absorption at room temperature are further increased. From the viewpoint, ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-heptadecene A structural unit derived from octadecene is preferable, a structural unit derived from ethylene, propylene, 1-butene, 1-hexene and 1-octene is more preferable, and a structural unit derived from ethylene and propylene is more preferable. The structural unit (A-ii) may be composed of a structural unit derived from one of these compounds, or may include a structural unit derived from two or more compounds.

  Examples of the structural unit (A-iii) include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1, 6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6 Derived from -chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, and 2-norbornadiene Contains structural units. Among these, from the ease of polymerization when producing the copolymer (A), and from the flexibility of the copolymer (A), stress relaxation at room temperature and stress absorption at room temperature, Structural units derived from 5-vinylnorbornene and 5-ethylidene-2-norbornene are preferred. The structural unit (A-iii) may be composed of a structural unit derived from one of these compounds, or may include a structural unit derived from two or more compounds.

  Examples of the other structural units include structural units derived from vinyl compounds having a cyclic structure including styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane, structural units derived from vinyl esters including vinyl acetate, and anhydrous maleic acid. Included are unsaturated organic acids including acids and derivatives thereof, and conjugated dienes including butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. The amount of the other structural unit is preferably 10 mol% or less, more preferably 5 mol% or less, substantially including 100 mol% of the entire copolymer (A). More preferably not.

  From the viewpoint of further improving the molding processability of the composition of the present invention, the intrinsic viscosity [η] of the copolymer (A) measured at 135 ° C. in a decalin solvent is 0.1 dl / g or more and 5.0 dl / g. g is preferably 0.5 dl / g or more and 4.0 dl / g or less, and more preferably 0.5 dl / g or more and 3.5 dl / g or less.

  From the viewpoint of further improving the flexibility and stress absorbability of the composition of the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer (A) measured by gel permeation chromatography (GPC). ) (Molecular weight distribution, Mw / Mn) is preferably 1.0 or more and 3.5 or less, more preferably 1.2 or more and 3.0 or less, and 1.5 or more and 2.5 or less. More preferably.

  From the viewpoint of further improving the mechanical strength such as workability and tensile elongation of the composition of the present invention, the weight average molecular weight (Mw) of the copolymer (A) measured by gel permeation chromatography (GPC) is polystyrene. It is preferably 500 or more and 10,000,000 or less in terms of conversion, preferably 1,000 or more and 5,000,000 or less, and more preferably 1,000 or more and 2,500,000 or less.

Lightweight and from the viewpoint of more enhancing compositions of the present invention, ASTM density of the copolymer as measured according to D 1505 (A) is preferably not more than 810kg / ^{m 3} or more 880 kg / ^{m 3} , more preferably not more than 820 kg / ^{m 3} or more 870 kg / ^{m 3,} more preferably more preferably, is 830 kg / ^{m 3} or more 855kg / ^{m 3} or less is at 820 kg / ^{m 3} or more 860 kg / ^{m 3} or less More preferably.

  From the viewpoint of further enhancing the flexibility of the composition of the present invention, the copolymer (A) after 15 seconds from the start of pressing needle contact, measured in the state of a 3 mm-thick press sheet according to JIS K6253. The Shore A hardness is preferably 5 or more and 95 or less, more preferably 10 or more and 95 or less, further preferably 25 or more and 90 or less, and particularly preferably 50 or more and 90 or less.

  From the viewpoint of further improving the stress relaxation property and shape followability of the composition of the present invention, the push needle of the copolymer (A) measured in the state of a press sheet having a thickness of 3 mm in accordance with JIS K6253. The change ΔHS between the Shore A hardness value immediately after the start of contact and the Shore A hardness value 15 seconds after the start of contact with the push needle is preferably 10 or more and 60 or less, and preferably 10 or more and 50 or less. Is more preferably 15 or more and 45 or less.

Note that ΔHS is a value obtained according to the following equation.
ΔHS = (Shore A hardness value immediately after start of pressing needle contact−Shore A hardness value 15 seconds after start of pressing needle contact)

  From the viewpoint of reducing the width of the composition distribution to reduce the amount of low molecular weight components and making it difficult to cause molding defects due to stickiness caused by the low molecular weight components, the extraction amount of the copolymer (A) with methyl acetate is 0. The mass is preferably from 1.5% by mass to 1.5% by mass, more preferably from 0% by mass to 1.0% by mass, and still more preferably from 0% by mass to 0.8% by mass. More preferably, it is at least 0.7% by mass.

  The amount extracted into methyl acetate is measured, for example, as the amount of change in the mass of copolymer (A) before and after extraction when the components contained in copolymer (A) are extracted into methyl acetate by the Soxhlet extraction method. Can do.

  From the viewpoint of further improving the heat resistance of the composition of the present invention, the melting point (Tm) of the copolymer (A) measured by a differential scanning calorimeter (DSC) (hereinafter referred to as the weight measured by DSC in the present invention). The melting point of the coalescence represents the melting point (Tm).) Is not observed or is preferably less than 135 ° C. From the above viewpoint, the melting point (Tm) is not observed or is more preferably less than 110 ° C.

  From the viewpoint of further increasing the stress absorbability of the composition of the present invention, the co-weight obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of −40 to 150 ° C. The tan δ peak value of the union (A) is preferably 1.0 or more and 5.0 or less, more preferably 1.5 or more and 5.0 or less, and 2.0 or more and 4.0 or less. Is more preferable.

  The tan δ peak value of the copolymer (A) can be set to a temperature closer to room temperature than that of the styrenic copolymer. Therefore, when the tan δ value at room temperature is further increased and the composition of the present invention is used, a higher tan δ peak value is obtained at room temperature, so that the vibration damping property can be improved.

  From the viewpoint of further enhancing the room temperature stress absorbability of the composition of the present invention, it is obtained by performing dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −40 to 150 ° C. The tan δ peak temperature of the copolymer (A) is preferably 0 ° C. or higher and 40 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 20 ° C. or higher and 40 ° C. or lower. More preferably, the temperature is 25 ° C. or higher and 40 ° C. or lower.

  The tan δ peak temperature of the copolymer (A) can be set to a temperature closer to room temperature than that of the styrenic copolymer. Therefore, the value of tan δ at room temperature can be further increased, and the vibration damping property at room temperature of the composition of the present invention can be improved.

(Production method of copolymer (A))
The production method of the copolymer (A) is not particularly limited. For example, 4-methyl-1-pentene and the above-mentioned “monomer leading to the structural unit (ii)” are polymerized in the presence of a suitable polymerization catalyst. Can be obtained. Here, as a polymerization catalyst that can be used in the present invention, a conventionally known catalyst such as a magnesium-supported titanium catalyst, WO 01/53369, WO 01/27124, JP-A-3-19396, or The metallocene catalyst described in JP-A No. 02-41303 is preferably used, and more preferably, an olefin polymerization catalyst containing a metallocene compound represented by the following general formula (1) or (2) is preferably used. It is done.

In the general formulas (1) and (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ And R ¹⁴ is selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R ¹ to R ⁴ are bonded to each other to form a ring. The adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and A may contain a partially unsaturated bond and / or an aromatic ring. A divalent hydrocarbon group of ˜20, and A may include two or more ring structures including a ring formed with Y;
M is a metal selected from Group 4 of the periodic table,
Y is carbon or silicon;
Q is selected from the same or different combinations from halogen, hydrocarbon groups, and anionic ligands or neutral ligands capable of coordinating with lone pairs;
j is an integer of 1-4.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and the above general formula (1) or (2) R ¹⁴ is selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different.

  The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. Yes, it may contain one or more ring structures. Moreover, a part or all of hydrogen of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group, or a fluorine-containing hydrocarbon group. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, and 1-ethyl-1. -Methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl -1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, Naphthyl, tolyl, chlorophenyl, chlorobipheny , Chloronaphthyl, and the like.

  The silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like. Is mentioned.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , and R ⁸ = R ^9. And the fluorene ring is more preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 3rd, 6th, 2nd and 7th positions on the fluorene ring correspond to R ⁷ , R ¹⁰ , R ⁶ and R ¹¹ , respectively.

R ¹³ and R ^{14 in} the general formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different from each other. Specific examples of preferred hydrocarbon groups include the same as those described above.

Y is carbon or silicon. In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include methylene, dimethylmethylene, diisopropylmethylene, methyl-tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenyl. Methylene, methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene, dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene , Dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, fluoromethyl Enirushiriren, chloromethyl silylene, diphenyl silylene, mention may be made of di -p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferred examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanidene. Examples include lidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

  M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.

  Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, and an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, and tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

  In the general formulas (1) and (2), j is preferably 2.

  As the metallocene compound constituting the olefin polymerization catalyst that can be used in the present invention, the metallocene compound represented by the above general formula (1) or (2) is particularly preferably exemplified, but is not limited thereto. For example, other suitable examples of metallocene compounds that can be used in the present invention include metallocene compounds represented by the following general formula [I].

In the general formula [I], R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each Independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, R ² is a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and R ⁴ is a hydrogen atom; Of the substituents from R ¹ to R ¹⁶ excluding R ⁴ , any two substituents may be bonded to each other to form a ring, M is a Group 4 transition metal, and Q is a halogen atom. , A hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, j is an integer of 1 to 4, and when j is an integer of 2 or more, Q is the same or You may choose a different combination.

In the general formula [I], R ¹ and R ³ are preferably hydrogen atoms; R ² is preferably a hydrocarbon group having 1 to 20 carbon atoms, and 3 carbons are bonded to the cyclopentadienyl ring. It is preferably a substituent which is a secondary carbon; R ⁵ and R ⁷ are preferably bonded to each other to form a ring; R ⁹ , R ¹² , R ¹³ and R ¹⁶ are each a hydrogen atom. Preferably, R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ are hydrocarbon groups, or R ¹⁰ and R ¹¹ are bonded to each other to form a ring, and R ¹⁴ and R ¹⁵ are bonded to each other to form a ring It is preferable to form.

In the general formula [I], examples of the hydrocarbon group that can be R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic saturated hydrocarbon group. , A cyclic unsaturated hydrocarbon group, or a group obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. Carbon number of a hydrocarbon group is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

  Examples of the linear hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. And linear alkyl groups such as n-decanyl group; linear alkenyl groups such as allyl group.

  Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

  Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

  Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, and a triphenylmethyl group. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

Examples of the hetero atom-containing hydrocarbon group in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an oxygen atom such as a furyl group -Containing hydrocarbon group; N-methylamino group, N, N-dimethylamino group, amino group such as N-phenylamino group, nitrogen atom-containing hydrocarbon group such as pyryl group; sulfur atom-containing hydrocarbon group such as thienyl group Is mentioned. Carbon number of a hetero atom containing hydrocarbon group is 1-20 normally, Preferably it is 2-18, More preferably, it is 2-15. However, the silicon-containing group is excluded from the heteroatom-containing hydrocarbon group.

Examples of the silicon-containing group in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, a formula —SiR ₃ such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. In the formula, a plurality of R's are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.

Of the substituents from R ¹ to R ¹⁶ excluding R ⁴ , two adjacent substituents (eg, R ¹ and R ² , R ² and R ³ , R ⁵ and R ⁷ , R ⁶ and R ⁸ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ) are bonded together to form a ring. R ⁶ and R ⁷ may be bonded to each other to form a ring, R ¹ and R ⁸ may be bonded to each other to form a ring, and R ³ and R ⁵ may be bonded to each other It may combine to form a ring. Two or more ring formations may exist in the molecule.

  In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a hetero ring such as a furan ring and a thiophene ring and a corresponding hydrogenated hetero ring, preferably a cyclohexane ring; a benzene ring and a hydrogen Benzene ring. Such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ and R ³ are preferably hydrogen atoms from the viewpoint of stereoregularity.

At least one selected from R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably R ⁵ is a hydrocarbon group, ⁵ is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and R ⁵ is an alkyl group having 2 or more carbon atoms. Especially preferred. From the viewpoint of synthesis, R ⁶ and R ⁷ are preferably hydrogen atoms. R ⁵ and R ⁷ are more preferably bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring.

R ⁸ is preferably a hydrocarbon group, and particularly preferably an alkyl group.

R ² is preferably a hydrocarbon group from the viewpoint of stereoregularity, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, and a linear hydrocarbon. Group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable. preferable.

Specific examples of R ² include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. Is a substituent such as a tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group or the like, in which the carbon having a free valence is a tertiary carbon, particularly preferably a tert-butyl group, 1- An adamantyl group;

In general formula [I], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably from the viewpoint of stereoregularity and molecular weight. Is a hydrogen atom.

R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, still more preferably It is a C1-C20 hydrocarbon group.

R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3 6,7,8,10-hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1 ′, 1 ′, 3 ′, 6 ′, 8 ′, 8′-hexamethyl-1′H, 8′H-dicyclopenta [B, h] fluorenyl group is exemplified, and 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- is particularly preferred. 1H-dibenzo [b, h] fluorenyl group.

  In the general formula [I], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

  In the general formula [I], examples of the halogen atom that can be Q include fluorine, chlorine, bromine, and iodine.

Examples of the hydrocarbon group that can be Q include the same groups as the hydrocarbon groups in R ^{1 to} R ¹⁶ (excluding R ⁴ ), preferably alkyls such as linear alkyl groups and branched alkyl groups. It is a group.

  Examples of the anion ligand in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; dimethylamide and diisopropylamide Amide groups such as methylanilide and diphenylamide.

  Examples of the neutral ligand capable of coordinating with a lone pair in Q include, for example, organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2- Examples include ethers such as dimethoxyethane.

  It is preferable that at least one Q is a halogen atom or an alkyl group.

  In the general formula [I], j is preferably 2.

  The position number used for naming the compound [I] is [1- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [ b, h] fluoren-12′-yl) (5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)] zirconium dichloride, and [8- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluoren-12'-yl) (2-tert-butyl-8-methyl) -3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)] zirconium dichloride as an example, one of the enantiomers is represented by formula [I-1], I-2].

  Specific examples of the metallocene compound include compounds exemplified in WO 01/27124, WO 2006/025540, or WO 2014/050817. The range is not limited.

When a metallocene compound is used for the production of the copolymer (A), the catalyst component is
(A) a metallocene compound (for example, a metallocene compound represented by the above general formula (1), (2) or [I]);
(B) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the metallocene compound (a) to form an ion pair, and (b-3) at least one selected from organoaluminum compounds A compound,
If necessary,
(C) It is comprised from a particulate carrier. As a manufacturing method, for example, a method described in International Publication No. 01/27124 can be employed.

  Further, it reacts with an organoaluminum oxy compound (b-1) (hereinafter also referred to as “component (b-1)”) and a metallocene compound (a) (hereinafter also referred to as “component (a)”) to form an ion pair. Specifics of compound to be formed (hereinafter also referred to as “component (b-2)”), organoaluminum compound (b-3) (hereinafter also referred to as “component (b-3)”), and particulate carrier (c) Examples include those compounds or carriers conventionally known in the field of olefin polymerization, such as the specific examples described in WO 01/27124.

  Here, in a preferred embodiment of the present invention, the copolymer (A) polymerizes 4-methyl-1-pentene and the above-mentioned “monomer leading to the structural unit (ii)” in the presence of the polymerization catalyst. However, in the production of the copolymer (A), the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

  In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent constituting the liquid phase. Specific examples of such inert hydrocarbons include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof.

  It is also possible to carry out bulk polymerization using 4-methyl-1-pentene and the above-mentioned “monomer leading to the structural unit (ii)” itself as a solvent.

  Moreover, composition distribution was controlled by carrying out the homopolymerization of 4-methyl-1-pentene and the copolymerization of 4-methyl-1-pentene and the above-mentioned “monomer leading to structural unit (ii)” stepwise. It is also possible to obtain a copolymer (A).

In carrying out the polymerization, the component (a) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol in terms of Group 4 metal atom in the periodic table per liter of reaction volume. Used in various amounts. In the component (b-1), the molar ratio [(b-1) / M] of the component (b-1) and the transition metal atom (M) in the component (a) is usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. In the component (b-2), the molar ratio [(b-2) / M] of the component (b-2) and the transition metal atom (M) in the component (a) is usually 1 to 10, preferably 1. Used in an amount such that it is ˜5. Component (b-3) has a molar ratio [(b-2) / M] of component (b-3) to transition metal atom (M) in component (a) of usually 10 to 5000, preferably 20 It is used in an amount such that it is ˜2000.

  The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 100 ° C.

  The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  Hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer during the polymerization, and the amount thereof is 0.000 per 1 kg in total of 4-methyl-1-pentene and the above-mentioned “monomer leading to the structural unit (ii)”. About 001 to 100NL is appropriate.

1-2. Composition (B)
The composition (B) includes a structural unit derived from ethylene (B-i), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (B-ii), and a structural unit derived from a non-conjugated polyene ( A thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing a copolymer (B-I) containing B-iii) and a polyolefin resin (B-II). The composition (B) may contain components other than the copolymer (BI) and the polyolefin resin (B-II) as long as the effects of the present invention are exhibited.

  The mass ratio (copolymer (B-)) of the copolymer (BI) and the polyolefin resin (B-II) contained in the composition (B) and the mixture for producing the composition (B). The mass of I) / the mass of the polyolefin resin (B-II), hereinafter simply referred to as “(BI) / (B-II)”) is preferably 90/10 to 5/95, More preferably, the ratio is 70/30 to 10/90.

  Dynamic cross-linking means heat treatment while kneading the mixture in a molten state. The composition (B) and the mixture may further contain a crosslinking agent, a crosslinking aid, a softening agent and other components for dynamic crosslinking.

  The composition (B) has a sea-island structure including an island part containing the copolymer (BI) and a sea part containing the polyolefin resin (B-II).

1-2-1. Copolymer (BI)
The copolymer (BI) is derived from a structural unit (Bi) derived from ethylene, a structural unit (B-ii) derived from an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. An ethylene / α-olefin / non-conjugated polyene copolymer containing a structural unit (B-iii).

  Molar ratio of the structural unit (Bi) and the structural unit (B-ii) contained in the copolymer (BI) (molar amount of the structural unit (Bi) / structural unit (B-ii)) The molar amount, hereinafter simply referred to as “(B-i) / (B-ii)”) is preferably 50/50 to 95/5, and preferably 60/40 to 80/20. More preferably, it is more preferably 65/35 to 75/25.

  Examples of the structural unit (B-ii) include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12- Structural units derived from ethyl-1-tetradecene are included. Among these, from the viewpoint of further increasing the mechanical strength, structural units derived from propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and structural units derived from propylene are further included. preferable. The structural unit (B-ii) may be composed of a structural unit derived from one of these compounds, or may include a structural unit derived from two or more compounds.

  Examples of the structural unit (B-iii) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4, Chain unconjugated comprising 5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene Diene, methyltetrahydroindene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-iso Propenyl-2-norbornene, 5-vinyl-2-norbornene (VNB), 5-isopropenyl-2-norbornene, 5-iso Cyclic non-conjugated dienes including tenenyl-2-norbornene, cyclopentadiene, and norbornadiene, and 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2 , 2-norbornadiene, and structural units derived from triene including 4-ethylidene-8-methyl-1,7-nanodiene. Among these, from the viewpoint of increasing the crosslinking efficiency, structural units derived from 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable. The structural unit (B-iii) may be composed of a structural unit derived from one of these compounds, or may include a structural unit derived from two or more compounds.

  From the viewpoint of further improving rubber elasticity, mechanical strength, and moldability, the iodine value of the copolymer (BI) is preferably 1 or more and 50 or less, more preferably 5 or more and 40 or less, More preferably, it is 10 or more and 30 or less. The iodine value can be used as an index of the amount of the structural unit (B-iii) contained in the copolymer (BI).

  From the viewpoint of further improving rubber elasticity, hardness, low-temperature flexibility and mechanical strength, the amount of the structural unit (B-iii) contained in the copolymer (BI) is determined according to the copolymer (BI). It is preferable that they are 2 mass% or more and 20 mass% or less with respect to the total mass of.

  From the viewpoint of further improving mechanical strength such as tensile elongation of the composition of the present invention and molding processability, the intrinsic viscosity [η] of the copolymer (BI) measured in a decalin solvent at 135 ° C. is: It is preferably 1.0 dl / g or more and 10.0 dl / g or less, and more preferably 1.5 dl / g or more and 8.0 dl / g or less.

  From the viewpoint of further improving mechanical strength and moldability, the Mooney viscosity (ML1 + 4 (100 ° C.)) of the copolymer (BI) measured according to JIS 6300-1 is 10 or more and 250 or less. It is preferable that it is 30 or more and 150 or less.

  The copolymer (BI) may be a so-called oil-extended rubber in which a softener, preferably a mineral oil softener, is blended during the production. Examples of the mineral oil softener include known mineral oil softeners such as paraffin process oil.

1-2-2. Polyolefin resin (B-II)
The polyolefin resin (B-II) is an α-olefin homopolymer or a copolymer containing an α-olefin. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. The copolymer is a copolymer having a content of α-olefin having the largest molar amount of 90 mol% or more.

  From the viewpoint of further improving the heat resistance of the composition of the present invention, the melting point (Tm) of the polyolefin resin (B-II) is preferably 70 ° C. or higher and 200 ° C. or lower, and preferably 80 ° C. or higher and 170 ° C. or lower. More preferred.

  From the viewpoint of further improving heat resistance and moldability, the polyolefin resin (B-II) is more preferably a propylene polymer. At this time, the polyolefin resin (B-II) may contain a polyolefin resin other than the propylene-based polymer.

1-2-2-1. Propylene Polymers Propylene polymers are propylene homopolymers, random copolymers of propylene and other α-olefins, or propylene homopolymers and amorphous or low crystalline propylene / ethylene random copolymers. It is a block copolymer with a polymer. Examples of the other α-olefins include ethylene, 1-butene, 1-pentene and 4-methyl-1-pentene. The amount of the other α-olefin in the propylene polymer is preferably 10 mol% or less.

  From the viewpoint of further improving the heat resistance of the composition of the present invention, the melting point of the propylene-based polymer is preferably 120 ° C. or higher and 170 ° C. or lower, and more preferably 145 ° C. or higher and 165 ° C. or lower.

  The propylene-based polymer may have an isotactic structure, may have a syndiotactic structure, may be a mixture of these structures, or may contain a part of an atactic structure in addition to these. Good.

  From the viewpoint of further improving the fluidity and moldability, the melt flow rate (MFR) of the propylene polymer measured at a temperature of 230 ° C. and a load of 21.18 N is 0.05 g / 10 min in accordance with JIS K6758. It is preferably 100 g / 10 min or less, more preferably 0.1 g / 10 min or more and 50 g / 10 min or less.

(Propylene polymer production method)
The propylene polymer can be produced by polymerizing the above components by a known method.

  The propylene-based polymer may be a commercial product manufactured and sold as a polypropylene resin.

1-2-3. Crosslinking agent Examples of the crosslinking examples include phenolic vulcanizing agents including organic peroxides, sulfur, sulfur compounds, and phenolic resins.

  Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl 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 peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, Diase Ruperuokishido include lauroyl peroxide, and tert- butyl cumyl peroxide.

  Of these, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di has a low odor and is less likely to cause scorch. (Tert-Butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4 1,4-bis (tert-butylperoxy) valerate is preferred, and 1,3-bis (tert-butylperoxyisopropyl) benzene is more preferred.

  From the viewpoint of making dynamic cross-linking more likely to occur and making it easy to adjust the heat resistance, tensile properties and rubber elasticity of the molded product to desired ranges, the content of the cross-linking example is copolymer (BI). When the content of the polyolefin resin (B-II) is 100 parts by mass, it is preferably 0.01 parts by mass or more and 15 parts by mass or less, and preferably 0.03 parts by mass or more and 12 parts by mass or less. More preferred.

1-2-4. Cross-linking aid Cross-linking aid can form cross-linking points uniformly and make it difficult to cause a rapid reaction.

  Examples of the crosslinking aid include sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, and trimethylolpropane- Crosslinking aids including N, N'-m-phenylene dimaleimide, and divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate A cross-linking co-agent consisting of a polyfunctional methacrylate monomer containing or a polyfunctional vinyl monomer containing vinyl butyrate and vinyl stearate is included. Of these, divinylbenzene is easy to handle, highly compatible with the copolymer (BI) and the polyolefin resin (B-II), and has organic peroxide as the crosslinking agent. In order to promote the dispersion of the product, it is easy to obtain an elastomer composition (B) in which crosslinking points are uniformly formed and both the fluidity and physical properties are high.

  From the above viewpoint, the content of the crosslinking aid is 0.01 parts by mass or more and 15 parts by mass or less when the contents of the copolymer (I) and the polyolefin resin (II) are 100 parts by mass. Is preferably 0.03 parts by mass or more and 12 parts by mass or less.

1-2-5. Softening agent The softening agent can increase the fluidity of the material during dynamic crosslinking and can adjust the hardness of the composition (B) to a desired level.

  Examples of the softeners include process oils, lubricating oils, paraffins, liquid paraffins, polyethylene waxes, polypropylene waxes, petroleum asphalts, and petroleum softeners including petroleum jelly, coal tar, and coal tar softeners including coal tar pitch. Oil, softeners including castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil, waxes including tall oil, sub, factis, beeswax, carnauba wax and lanolin, ricinoleic acid, palmitic acid, stearin Synthetic polymers including acids, fatty acids or fatty acid salts including barium stearate, calcium stearate, and zinc laurate, naphthenic acid, pine oil, rosin or derivatives thereof, terpene resins, petroleum resins, coumarone indene resins and atactic polypropylene. material, Ester softeners including octyl phthalate, dioctyl adipate, and dioctyl sebacate, microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal modified polyisoprene, hydrogenated terminal modified polyisoprene, liquid thiocol, and hydrocarbons System synthetic lubricating oil and the like. Among these, from the above viewpoint, petroleum-based softeners are preferable, and process oil is more preferable.

  From the above viewpoint, the content of the softening agent is preferably 10 parts by mass or more and 200 parts by mass or less, and 15 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the copolymer (BI). More preferably, it is more preferably 20 parts by mass or more and 80 parts by mass or less.

1-2-6. Other components The composition (B) and the mixture for producing the composition (B) are provided with a slip agent, a nucleating agent, a filler, an antioxidant and a weathering stabilizer as long as the effects of the present invention are exhibited. , Colorants, and other components including foaming agents.

  Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents. Examples of the non-melting crystallization nucleating agent include inorganic substances including talc, mica, silica, and aluminum, as well as brominated biphenyl ether, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), and organic phosphates. , Rosin based crystallization nucleating agents, substituted triethylene glycol terephthalate and organic materials including Terylene & Nylon fibers.

  Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.

  Examples of the filler include carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, and glass fiber.

1-2-7. Method for Producing Composition (B) The composition (B) comprises a mixture containing the copolymer (BI) and the polyolefin resin (B-II) in the presence of the crosslinking agent or the crosslinking agent and the It can be produced by dynamic crosslinking in the presence of a crosslinking aid. The mass ratio [(BI) / (B-II)] of the copolymer (BI) and the polyolefin resin (B-II) in the above mixture can be 90/10 to 5/95. 70/30 to 10/90.

The kneading and heat treatment for dynamic crosslinking are preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of the heat treatment can be in the range of 300 ° C. or less from the melting point of the copolymer (B), preferably in the range of 150 ° C. or more and 270 ° C. or less, and in the range of 170 ° C. or more and 250 ° C. or less. It is more preferable that The kneading time can be from 1 minute to 20 minutes, and more preferably from 1 minute to 10 minutes. Shear force applied to the molten mixture by kneading, may be a 10 sec ^-1 or more 50,000Sec ^-1 or less at a shear ^rate, it is preferable to 100sec ^-1 10,000sec -1.

  The kneading can be performed by a known apparatus including a mixing roll, an intensive mixer (for example, a Banbury mixer or a kneader), a single screw extruder, and a twin screw extruder. It is preferable to carry out by the apparatus.

<Other resins (C)>
Other resin (C) may be added to the thermoplastic polymer composition for vibration damping material of the present invention as long as the excellent properties of the copolymer (A) are not impaired. The amount added is generally 50% by weight or less, preferably 40% by weight or less for the composition. Examples of other resins (C) include olefin polymers other than the copolymer (A), polyesters, polyamides, modified olefin polymers, and the like.

  Examples of the olefin polymer include those obtained by polymerizing one or more olefins selected from linear or branched α-olefins having 2 to 20 carbon atoms. Examples of the linear or branched α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene and 3-methyl-1- Examples include pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. Among these, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  In addition to the α-olefin described above, the olefin polymer is a cyclic olefin, a functionalized vinyl compound, a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.) and a polymerizing polymer within the range not impairing the object of the present invention. A monomer having a carbon-carbon double bond (hereinafter also referred to as a polar group-containing monomer), a conjugated diene, a non-conjugated polyene, or the like may be included as a comonomer.

  Cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5. , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  Examples of functionalized vinyl compounds include aromatic vinyl compounds and alicyclic vinyl compounds. Examples of the aromatic vinyl compound include mono- or poly-styrene such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene. Functional group-containing styrene derivatives such as alkyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene; and 3-phenylpropylene, 4 -Phenylpropylene, α-methylstyrene and the like. Examples of the alicyclic vinyl compound include vinylcyclohexane and vinylcycloheptane.

  The functionalized vinyl compound may be a homopolymer of the functionalized vinyl compound or a copolymer with a copolymer component. Specific examples of copolymer components include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid, unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, sodium methacrylate, acrylic Unsaturated carboxylic acid salts such as sodium acetate, unsaturated carboxylic acid esters such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, etc. Examples include, but are not limited to, saturated carboxylic acid amides. These copolymerization components may use only 1 type and may use 2 or more types together.

  Examples of the polyester include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compounds such as bisphenol. And aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, hexahydroterephthalic acid, etc. A crystalline thermoplastic resin formed from the alicyclic dicarboxylic acid or two or more dicarboxylic acids selected from these alicyclic dicarboxylic acids. The polyester may be modified with a small amount of trihydroxy or higher polyhydroxy compound such as triol or tricarboxylic acid, polycarboxylic acid or the like as long as it exhibits thermoplasticity. Specific examples of this polyester include polylactic acid, polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolymer, and the like.

  Examples of the polyamide include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis (aminomethyl). ) Diamines such as cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, alicyclic diamine or aromatic diamine, and adipic acid, suberic acid, sebacic acid, cyclohexane Polyamides obtained by polycondensation with dicarboxylic acids such as aliphatic dicarboxylic acids such as dicarboxylic acid, terephthalic acid and isophthalic acid, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, ε-aminocaproic acid, 11-aminoundecanoic acid, etc. Obtained by condensation of aminocarboxylic acid Polyamides, .epsilon.-caprolactam, .omega. polyamides obtained from lactams laurolactam such or copolymerized polyamide composed of these ingredients, more like a mixture of these polyamides. Specific examples of the polyamide include nylon 6, nylon 66, nylon 6110, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, and aromatic nylon.

<Other additives>
Other additives for resin can be arbitrarily added to the resin composition of the present invention within a range that does not impair the effects of the present invention, depending on the application. Examples of such additives for resins include pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and weathering stability. Agent, heat stabilizer, anti-slip agent, anti-blocking agent, foaming agent, foaming aid, crystallization aid, antifogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent , Co-crosslinking agents, crosslinking aids, pressure-sensitive adhesives, softeners, processing aids and the like. These additives can be used singly or in appropriate combination of two or more.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. Although the addition amount of these pigments and dyes is not particularly limited, the total amount is usually 5 parts by mass or less, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the copolymer (A).

  Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.

  Examples of the lubricant include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), training fatty acid salts (such as calcium stearate), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), and the like.

  Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

  Antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.) Phosphorus-based (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate etc.), amine-based (N, N-diisopropyl-p-phenylenediamine etc.) antioxidants Can be mentioned.

  Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above surfactants, fatty acid esters, and polymer antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  The addition amount of various additives such as the above fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and the like impairs the purpose of the present invention. Although it does not specifically limit according to a use within the range which is not, It is preferable that it is 0.01-30 weight% with respect to the said 4-methyl- 1-pentene type polymer, respectively.

1-3. Manufacturing method of composition of this invention The composition of this invention can be manufactured by the method of mixing a copolymer (A) and a composition (B) mechanically by a well-known method, for example. After mixing, the mixture may be melt-kneaded using an extruder.

  In addition, the said mixing may mix with a copolymer (A), after obtaining a composition (B), or a copolymer (BI) and polyolefin resin (B-II) are made dynamic. During the crosslinking, the copolymer (A) may be added simultaneously and kneaded.

  The optionally used crosslinking agent, crosslinking aid and softening agent may be mixed in advance with any of the components, or when the composition (B) and the copolymer (A) are mixed, When the polymer (BI) and the polyolefin resin (B-II) are dynamically crosslinked, they may be injected into the system.

  In addition, you may manufacture the composition of this invention using the said method together.

2. Molded body The composition of the present invention can be formed into a molded body containing the composition of the present invention by a known molding method.

  Examples of the molding method include an extrusion molding method, a press molding method, an injection molding method, a calendar molding method, and a hollow molding method. Further, the composition of the present invention may be formed into a sheet shape by these forming methods, and then the obtained sheet-shaped formed body may be subjected to secondary processing by a thermoforming method or the like, The molded body may be laminated with other materials.

  Examples of the substrate that can be used for the lamination include cloth, resin, rubber, and wood. Examples of the fabric include cotton, hemp, wool, rayon, polyester, nylon, vinylon, polypropylene, polyethylene, acrylic, aramid, and a woven fabric, a knitted fabric, and a nonwoven fabric including carbon-based fibers. Examples of the resin include a thermoplastic resin and a thermosetting resin. Suitable examples of the rubber include thermoplastic elastomers and thermosetting elastomers (including vulcanized rubber) formed into a film or sheet. The above lamination can be performed via an adhesive, but when laminating with polyethylene or polypropylene, the adhesive may not be used and the layers may be laminated by heat fusion.

  The said molded object is used suitably as a damping material. Examples of the damping material include a damping member, a shock absorbing material, a vibration absorbing material, and a resonance absorbing material. In particular, since the molded article has high stress absorbability at room temperature, it is suitable for various known applications such as vibration damping materials used at room temperature, specifically automotive parts, civil engineering / building materials, and hygiene products.

<Auto parts>
Examples of the automobile parts that can be used in the molded article of the thermoplastic polymer composition of the present invention include weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, air duct hoses, cup holders, and side brake grips. , Shift knob cover, seat adjustment knob, flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot, glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter window gasket, corner molding, glass end Capsule, food seal, glass run channel, secondary seal, various packings, bumper parts, body panel, side shield, glass lunch Examples include channels, instrument panel skins, door skins, ceiling skins, weatherstrip materials, hoses, steering wheels, boots, wire harness covers, seat adjuster covers, and the like.

<Civil engineering / building materials>
Civil engineering / building materials that can be used in the molded thermoplastic polymer composition of the present invention include, for example, ground improvement sheets, waterworks, noise / vibration prevention walls and other civil engineering materials and construction materials, and various civil engineering / architecture gaskets. Examples thereof include vibration suppressing grip materials used for rotating devices such as sheets, water-stopping materials, joint materials, architectural window frames, and electric drills.

<Hygiene products>
Examples of sanitary products that can be used for the thermoplastic polymer composition molded article of the present invention include sanitary products such as sanitary products, disposable diapers, and toothbrush grips.

  EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

1. Measurement conditions, etc. The measurement conditions of the physical properties in the examples are as follows.

〔composition〕
The 4-methyl-1-pentene and α-olefin content in the 4-methyl-1-pentene / α-olefin copolymer (A) was measured by ¹³ C-NMR using the following apparatus and conditions. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20 vol%) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus 13C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, and 27.50 ppm is the reference value for chemical shift As measured.

〔density〕
The density of the copolymer (A) was calculated from the weight of each sample measured in water and in air using ALFA MIRAGE electronic hydrometer MD-300S according to ASTM D 1505 (in-water replacement method).

[Intrinsic viscosity]
The intrinsic viscosity [η] of the copolymer (A) was measured at 135 ° C. using a decalin solvent.

[Molecular weight (Mw, Mn), molecular weight distribution (Mw / Mn)]
The molecular weight of the copolymer (A) was measured using a liquid chromatograph: Waters ALC / GPC 150-C plus (integrated refractometer detector), and two columns of GMH6-HT manufactured by Tosoh Corporation and GMH6. -Two HTLs were connected in series, and o-dichlorobenzene was used as a mobile phase medium, and measurement was performed at a flow rate of 1.0 ml / min and 140 ° C.

  Mw / Mn value and Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.

[Heat resistance (melting point (Tm))]
The melting point (Tm) of the copolymer (A) was measured with a differential scanning calorimeter (DSC) using a DSC220C apparatus manufactured by Seiko Instruments Inc. Samples 7-12 mg obtained from the polymerization were sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes to completely melt and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the sample was heated again to 200 ° C. at 10 ° C./min. The peak temperature on the high temperature side in the endothermic curve in this second heating (second time) was adopted as the melting point (Tm).

[Flexibility (Shore A hardness)]
The Shore A hardness of the copolymer (A) and the composition is obtained by punching a sheet-like composition molded to a thickness of 2 mm, and stacking three of the punched sheet-like compositions to obtain a test piece for hardness measurement. This test piece was measured at 23 ° C. according to the description of test type A of “Durometer hardness test” in Section 6 of JIS K6253 (2006) “How to obtain vulcanized rubber and thermoplastic rubber-hardness”. went. The hardness of the test piece was measured immediately after the pressure plate was brought into contact with the test piece and 15 seconds after the contact. The hardness obtained immediately after the contact was referred to as “Shore A hardness (value immediately after measurement)”, and the hardness obtained 15 seconds after contact was referred to as “Shore A hardness (value after measurement 15 seconds)”.

[Stress relaxation (stress relaxation rate)]
The stress relaxation property of the composition was measured on a sample punched out to a length of 100 mm and a width of 10 mm from a 500 μm sheet-shaped composition. Using a universal tensile tester 3380 manufactured by Instron, the test piece was stretched 10% at a tensile speed of 200 mm / min. The stress at the time of stretching by 10% was measured, and the stretching was held as it was for 120 seconds. The change in stress at that time was measured, and the relaxation rate was calculated from the difference between the stress immediately after 10% elongation and the stress after 60 seconds.

[Stress absorption (dynamic viscoelasticity)]
The dynamic viscoelasticity of the copolymer (A) composition was measured using a viscoelasticity measuring device MCR301 (manufactured by Anton Paar). The temperature dependence of the viscosity of the sheet-like composition was measured under the following measurement conditions. The ratio (G ″ / G ′: loss tangent) between the storage elastic modulus (G ′) and the loss elastic modulus (G ″) obtained by the measurement was defined as tan δ. When tan δ is plotted against temperature, an upwardly convex curve, that is, a peak is obtained. The temperature at the peak apex is tan δ−Tg, and the maximum value at that temperature is measured. When two or more peaks were observed for tan δ, the tan δ-Tg value observed at 0 ° C. or higher and the tan δ-Tg value at 23 ° C. were recorded.

(Measurement condition)
Frequency: 1.6Hz
Temperature: -70 to 100 ° C
Ramp Rate: 2.0 ° C./min Strain: 0.5%

[Mechanical properties (elongation at break (EL) and stress at break (TS))]
The tensile elongation at break (EL) and the tensile stress at break (TS) of the composition were measured on No. 5 dumbbell test pieces described in JISK 7127, which were prepared by punching a sheet-like composition. Using this test piece, in accordance with the method specified in JISK 7127, a tensile test is performed under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 30 mm / min, and tensile elongation at break (EL) and tensile break stress (TS) are measured. It was measured.

[Vibration control (rebound resilience)]
The rebound resilience of the composition is a “Lupke rebound resilience test” in Section 4 of JIS K6255 (1996) “Rebound resilience test method for vulcanized rubber and thermoplastic rubber” for a composition molded to a thickness of 12 mm and a diameter of 29 mm. The measurement was performed at 23 ° C. in accordance with the description.

[Vibration control (calculation of loss factor by cantilever method)]
The loss factor of the composition was measured by a cantilever method tester (manufactured by Ono Sokki Co., Ltd.) at 23 ° C. in accordance with JIS K7391. As a measurement sample, a press sheet having a thickness of 1 mm was punched out to a width of 10 mm × 200 mm and pasted on a base layer made of SUS430, and vibration was performed by steady excitation using a non-contact electromagnetic vibrator. The loss factor of each material was calculated from the resonance frequency when the material vibrated.

2. Production of composition [4-methyl-1-pentene / α-olefin copolymer (A)]
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.13 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, 1 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride in terms of Al. The toluene solution containing 0.01 mmol of 0.34 ml of the solution was pressed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

  The obtained powdered polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer (hereinafter, also simply referred to as “polymer A-1”) was 36.9 g, the 4-methyl-1-pentene content in the polymer was 72.5 mol%, and the propylene content was 27. It was 5 mol%. Table 1 shows the physical properties of the obtained polymer.

[Thermoplastic elastomer composition (B)]
The following thermoplastic elastomer composition was used as the thermoplastic elastomer composition (B).

Composition B-1: Mitsui Chemical Co., Ltd., trade name: Miralastomer 8030NHS (a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing ethylene / propylene / ethylidene norbornene terpolymer rubber and polypropylene, Shore A hardness (immediately after) = 88, MFR (measured at a temperature of 230 ° C. and a load of 98 N) = 9.3 g / 10 minutes)
Composition B-2: Mitsui Chemical Co., Ltd., trade name: Miralastomer 5030NHS (a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing ethylene / propylene / ethylidene norbornene terpolymer rubber and polypropylene, Shore A hardness (immediately after) = 52, MFR (measured at a temperature of 230 ° C. and a load of 98 N) = 4.5 g / 10 minutes)

[Example 1]
10 parts by mass of the polymer A-1 and 90 parts by mass of the composition B-1 were mixed to obtain a thermoplastic polymer composition for damping material (Composition 1). For 100 parts by mass of composition 1, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer as a secondary antioxidant is added. 0.2 parts by mass was blended. Then, using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd., granulation was performed under the conditions of a set temperature of 250 ° C., a resin extrusion rate of 60 g / min and 200 rpm. And pelletized, and this was formed into a sheet to obtain a molded body 1. The composition and physical properties of the molded body 1 are shown in Table 2.

[Example 2]
25 parts by mass of Polymer A-1 and 75 parts by mass of Composition B-1 were mixed to obtain a thermoplastic polymer composition for vibration damping material (Composition 2). A molded body 2 was obtained in the same manner except that the composition 2 was used in place of the composition 1 of Example 1. The composition and physical properties of the molded body 2 are shown in Table 2.

[Example 3]
40 parts by mass of the polymer A-1 and 60 parts by mass of the composition B-1 were mixed to obtain a thermoplastic polymer composition for damping material (Composition 3). A molded body 3 was obtained in the same manner except that the composition 3 was used in place of the composition 1 of Example 1. The composition and physical properties of the molded body 3 are shown in Table 2.

[Example 4]
10 parts by mass of the polymer A-1 and 90 parts by mass of the composition B-2 were mixed to obtain a thermoplastic polymer composition for vibration damping material (composition 4). A molded body 4 was obtained in the same manner except that the composition 4 was used in place of the composition 1 of Example 1. The composition and physical properties of the molded body 4 are shown in Table 2.

[Example 5]
25 parts by mass of Polymer A-1 and 75 parts by mass of Composition B-2 were mixed to obtain a thermoplastic polymer composition for vibration damping material (Composition 5). A molded body 5 was obtained in the same manner except that the composition 5 was used in place of the composition 1 of Example 1. The composition and physical properties of the molded body 5 are shown in Table 2.

[Example 6]
40 parts by mass of Polymer A-1 and 60 parts by mass of Composition B-2 were mixed to obtain a thermoplastic polymer composition for vibration damping material (Composition 6). A molded body 6 was obtained in the same manner except that the composition 6 was used in place of the composition 1 of Example 1. The composition and physical properties of the molded body 6 are shown in Table 2.

[Comparative Example 1]
In Example 2, composition 7 was obtained in the same manner except that Kuraray Co., Ltd., trade name HIBLER 5127 (styrene-isoprene copolymer thermoplastic elastomer) was used instead of polymer A-1. A molded body 7 was obtained in the same manner except that the composition 7 was used instead of the composition 2 of Example 2. The composition and physical properties of the molded body 7 are shown in Table 3.

[Comparative Example 2]
In Example 2, S.A. manufactured by Asahi Kasei Chemicals Corporation was used instead of the polymer A-1. O. E. Composition 8 was obtained in the same manner except that S1605 (styrene-butadiene copolymer thermoplastic elastomer) was used. A molded body 8 was obtained in the same manner except that the composition 8 was used instead of the composition 2 of Example 2. The composition and physical properties of the molded body 8 are shown in Table 3.

[Reference Example 1]
A molded body 9 was obtained in the same manner as in Example 1, except that the composition B-1 was used without being mixed with other components in place of the composition 1. The composition and physical properties of the molded body 9 are shown in Table 3.

[Reference Example 2]
A molded body 10 was obtained in the same manner as in Example 1, except that the composition B-2 was used without being mixed with other components in place of the composition 1. Table 3 shows the composition and physical properties of the molded body 10.

  Molded bodies 1 to 1 obtained by molding a composition containing the copolymer (A) and the composition (B) in an amount such that the mass ratio (A) / (B) is 10/90 to 49/51. No. 6 was able to make tan δ at room temperature (23 ° C.) higher than that of molded bodies 7 and 8 obtained by molding a composition using a styrene polymer.

  Since the composition of the present invention has high stress absorbability at room temperature, it can be suitably used for applications such as vibration damping materials used at room temperature.

Claims (15)

Derived from at least one α-olefin selected from the structural unit (Ai) derived from 4-methyl-1-pentene and the α-olefin having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. A 4-methyl-1-pentene / α-olefin copolymer comprising a structural unit (A-ii) and optionally a structural unit (A-iii) derived from a non-conjugated polyene, When the total of (A-i), (A-ii) and (A-iii) is 100 mol%, the structural unit (A-i) is 63 to 86 mol%, and the structural unit (A-ii) is 4-methyl-1-pentene / α-olefin copolymer (A) containing 14 to 37 mol% and 0 to 10 mol% of the structural unit (A-iii);
A copolymer comprising a structural unit derived from ethylene (B-i), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (B-ii), and a structural unit derived from a non-conjugated polyene (B-iii). A thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing a polymer [BI] and a polyolefin resin [B-II],
The mass ratio (A) / (B) of the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B) is 10/90 to 49/51. A thermoplastic polymer composition for a vibration damping material.   The 4-methyl-1-pentene / α-olefin copolymer (A) is obtained when the total of the structural units (Ai), (A-ii) and (A-iii) is 100 mol%. 4-methyl- containing 63 to 80 mol% of the structural unit (A-i), 20 to 37 mol% of the structural unit (A-ii), and 0 to 10 mol% of the structural unit (A-iii). The thermoplastic polymer composition for a vibration damping material according to claim 1, which is a 1-pentene / α-olefin copolymer.   The 4-methyl-1-pentene / α-olefin copolymer (A) is a copolymer in which a melting point is not observed or a melting point is less than 135 ° C. 2. A thermoplastic polymer composition for a vibration damping material according to 2.   The 4-methyl-1-pentene / α-olefin copolymer (A) has a melting point not observed or is a copolymer having a temperature of less than 110 ° C. 2. A thermoplastic polymer composition for a vibration damping material according to item 1.   The thermoplastic polymer for a vibration damping material according to any one of claims 1 to 4, wherein the temperature at which the value of the loss tangent tan δ is maximized is a copolymer having a temperature of 0 ° C or higher and 40 ° C or lower. Composition.   The manufacturing method of a molded object including the process of shape | molding the thermoplastic polymer composition for damping materials of any one of Claims 1-5.   The manufacturing method according to claim 6, wherein the molded body is a vibration damping member.   The manufacturing method according to claim 6, wherein the molded body is an impact absorbing material.   The manufacturing method according to claim 6, wherein the molded body is a vibration absorbing material.   The manufacturing method according to claim 6, wherein the molded body is a resonance absorbing material.   The molded object containing the thermoplastic polymer composition for damping materials of any one of Claims 1-5.   The molded body according to claim 11, which is a vibration damping member.   The molded article according to claim 11, which is an impact absorbing material.   The molded body according to claim 11, which is a vibration absorbing material.   The molded article according to claim 11, which is a resonance absorbing material.