JPWO2014157502A1 - Thermoplastic polymer composition and use thereof - Google Patents

Abstract

An object of the present invention is to obtain a thermoplastic polymer composition suitable for obtaining a skin material that is excellent in stress relaxation property (shape followability) and flexibility, does not easily wrinkle when a substrate is applied, and has a good tactile sensation. In the present invention, the structural unit (i) derived from 4-methyl-1-pentene, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene A 4-methyl-1-pentene / α-olefin copolymer (A) containing a specific amount of a structural unit derived from an olefin (ii) and a structural unit derived from a non-conjugated polyene, ethylene / carbon atoms of 3 to 20 A thermoplastic elastomer composition (B) obtained by dynamically cross-linking a mixture containing an α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II], and a copolymer (A) And composition (B) The thermoplastic polymer composition according to claim 1, wherein the mass ratio (A) / (B) is 10/90 to 49/51.

Description

  The present invention relates to a thermoplastic polymer composition comprising 4-methyl-1-pentene / α-olefin copolymer and a thermoplastic elastomer composition, which are excellent in flexibility, tactile sensation, stress relaxation property, shape followability, and the like, and the same It depends on the application.

  Thermoplastic elastomers are lightweight and easy to recycle, so they are widely used as energy- and resource-saving elastomers, especially in automobile parts, industrial machine parts, electrical / electronic parts, building materials, etc. as an alternative to vulcanized rubber. Yes.

  Above all, polyolefin-based thermoplastic elastomers are made from crystalline polyolefins such as ethylene / propylene / non-conjugated diene copolymer (EPDM) and polypropylene, so they have a lighter specific gravity and heat resistance than other thermoplastic elastomers. Although it is excellent in durability such as aging and weather resistance, further improvements are required depending on applications.

  In the past, soft vinyl chloride resin was the mainstream for interior skin materials such as instrument panels and door trims for automobiles, but in recent years, olefin-based thermoplastic elastomers have begun to be used from the viewpoint of reducing the weight of materials. .

  Vacuum molding, especially convex vacuum forming, is common to shape interior skin sheets into the shape of instrument panels and door trims. Polyolefin thermoplastic elastomers also have a convex vacuum from the material side. Materials with excellent moldability are being developed. Recently, however, there has been a tendency to increase in vacuum forming, which is excellent in design properties, or stamping molding (low pressure molding), which has a relatively simple manufacturing process, and a polyolefin-based thermoplastic elastomer excellent in moldability is desired in these moldings. It is rare.

  Examples of methods for improving stamping moldability include polyolefin resin (A), ethylene / α-olefin copolymer rubber and / or ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), and propylene / ethylene copolymer weight. A method using an olefinic thermoplastic elastomer composition obtained by dynamically crosslinking a copolymer and / or a propylene / 1-butene copolymer (C) has been proposed (Japanese Patent Laid-Open No. 2001-171439: Patent Document 1).

  On the other hand, a 4-methyl-1-pentene / α-olefin copolymer containing 5-95 mol% of 4-methyl-1-pentene has been proposed as a polymer excellent in flexibility and stress relaxation properties (international publication). No. 2011/055803 pamphlet: Patent Document 2), 4-methyl-1-pentene / α-olefin copolymer may be mixed with crystalline polyolefin such as polypropylene or ethylene / α-olefin copolymer rubber. Have been described.

  Further, Patent Document 3 (Japanese Patent Laid-Open No. 2012-82401) proposes a 4-methyl-1-pentene / propylene copolymer containing 15 to 75 mol% of 4-methyl-1-pentene as a grip material. It describes that 4-methyl-1-pentene / propylene copolymer may be mixed with a thermoplastic resin such as polypropylene or rubber.

  In any case, however, there are still points to be improved for use in the skin material.

Japanese Patent Laid-Open No. 2001-171439 International Publication No. 2011/055803 Pamphlet JP 2012-82401 A

  An object of the present invention is to obtain a thermoplastic polymer composition suitable for obtaining a skin material that is excellent in stress relaxation property (shape followability) and flexibility, does not easily wrinkle when a substrate is applied, and has a good tactile sensation. is there.

The present invention relates to a structural unit (i) derived from 4-methyl-1-pentene: 63 to 86 mol%, at least one selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. Constituent unit (ii) derived from α-olefin of at least species: 14 to 37 mol% and constituent unit (iii) derived from non-conjugated polyene (provided that constituent unit (i), ( ii) 4-methyl-1-pentene / α-olefin copolymer (A) in which the total of (iii) and (iii) is 100 mol%,
A thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing an ethylene-carbon atom α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II]. Including
The thermoplastic polymer composition is characterized in that the mass ratio (A) / (B) of the copolymer (A) and the composition (B) is 10/90 to 49/51.

Further, the present invention is selected from structural units (i) derived from 4-methyl-1-pentene: 63 to 86 mol%, and an α-olefin having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. Constituent unit (ii) derived from at least one α-olefin: 14 to 37 mol% and constituent unit (iii) derived from non-conjugated polyene (provided that the constituent unit (i) 4-methyl-1-pentene / α-olefin copolymer (A), wherein the sum of (ii) and (iii) is 100 mol%),
A thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing an ethylene / carbon atom α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II],
A propylene-based polymer (C) having a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more and 90 to 100 mol% of a structural unit derived from propylene, and ,
Intrinsic viscosity [η] measured in decalin at 135 ° C. containing propylene-derived constitutional units in an amount of 40 to 89 mol% and carbon number 2 to 20 α-olefin-derived constitutional units in an amount of 11 to 60 mol%. MFR measured at (dl / g), 230 ° C., and load of 2160 g is the following relational expression: 1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20)
And a propylene copolymer (D) satisfying
The mass ratio (A) / [(B) + (C) + (D)] of the copolymer (A) and the composition (B) + polymer (C) + copolymer (D) is 10/90. It relates to a thermoplastic polymer composition characterized by being -49/51.

  Since the thermoplastic polymer composition of the present invention is excellent in stress relaxation (shape followability) and flexibility, when used in a skin material, it is difficult to become wrinkles and has excellent tactile sensation.

<4-Methyl-1-pentene / α-olefin copolymer (A)>
The 4-methyl-1-pentene / α-olefin copolymer (A), which is one of the components contained in the thermoplastic polymer composition of the present invention, is a structural unit derived from 4-methyl-1-pentene ( i): 63 to 86 mol%, preferably 63 to 80 mol%, more preferably 65 to 75 mol%, at least 1 selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene Structural unit derived from more than one α-olefin (ii): 14-37 mol%, preferably 20-37 mol%, more preferably 25-35 mol%, and structural unit derived from non-conjugated polyene (iii) It consists of 0 to 10 mol%, preferably 0 to 5 mol% (provided that the total of the structural units (i), (ii) and (iii) is 100 mol%).

  Specific examples of the α-olefin having 2 to 20 carbon atoms copolymerized with 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl- Suitable examples include 1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene and the like. It is done.

  Among these, from the viewpoint of the copolymerizability and the physical properties of the obtained copolymer, ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, 1-octadecene, and more preferably ethylene, propylene, 1-butene, 1-hexene, and 1-octene, and still more preferably ethylene , Propylene. These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more.

  Specific examples of the non-conjugated polyene copolymerized with 4-methyl-1-pentene include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 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-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2- Non-conjugated polyenes such as propenyl-2,2-norbornadiene , More preferably, 5-vinyl norbornene, 5-ethylidene-2-norbornene.

  The 4-methyl-1-pentene / α-olefin copolymer (A) contains structural units derived from other polymerizable compounds in addition to the α-olefin as long as the object of the present invention is not impaired. Also good.

  Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or the like Derivatives; conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and the like.

  In the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, the structural unit (i) derived from 4-methyl-1-pentene is in the above range. The combined composition is excellent in flexibility and stress relaxation property (shape followability) at room temperature.

  The 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention preferably has an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 0.1 to 5.0 dl / g. More preferably, it is in the range of 0.5 to 4.0 dl / g, more preferably 0.5 to 3.5 dl / g. When the intrinsic viscosity [η] is in the above range, a thermoplastic polymer composition having better moldability can be obtained.

  The 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention preferably has a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC). ) (Molecular weight distribution; Mw / Mn) is in the range of 1.0 to 3.5, more preferably 1.2 to 3.0, more preferably 1.5 to 2.5. When the molecular weight distribution is in the above range, a thermoplastic polymer composition having better tactile sensation can be obtained.

  The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention is in terms of polystyrene. Preferably it is 500-10,000,000, More preferably, it is 1,000-5,000,000, More preferably, it is 1,000-2,500,000.

The 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention preferably has a density (measured according to ASTM D 1505) of 880 to 810 kg / m ³ , more preferably 870 to 820 kg / m. ³ , more preferably 860 to 820 kg / m ³ , particularly preferably 855 to 830 kg / m ³ .

  When the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention is further made into a sheet, the Shore A hardness (according to JIS K6253) after 15 seconds from the start of pressing needle contact. The value of (measured in the state of a 3 mm thick press sheet) is desirably in the range of 5 to 90, preferably 10 to 85, and more preferably 15 to 80.

  When the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention is further formed into a sheet, the Shore A hardness defined by the following formula (according to JIS K6253, thickness: 3 mm) It is desirable that the change ΔHS of the value (measured in the state of the press sheet) is in the range of 10 to 60, preferably 10 to 50, more preferably 10 to 45.

ΔHS = (Shore A hardness value immediately after start of pressing needle contact−Shore A hardness value 15 seconds after start of pressing needle contact)
In the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, the extraction amount with methyl acetate is preferably 0 to 1.5% by mass, more preferably 0 to 1.0. It is desirable to be in the range of mass%, more preferably 0 to 0.8 mass%, particularly preferably 0 to 0.7 mass%.

  The amount of methyl acetate extracted is an index of stickiness during molding, and if this value is large, the resulting polymer has a large composition distribution and contains low molecular weight components, causing problems during molding. When the methyl acetate extraction amount is within the above range, there is no problem due to stickiness during molding.

  In the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, the melting point [Tm] measured by a differential scanning calorimeter (DSC) is not recognized, or the melting point [Tm ], It is preferable that it is less than 110 degreeC.

  The 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention is further subjected to dynamic viscoelasticity measurement at a frequency of 10 rad / s in a temperature range of −40 to 150 ° C. The maximum loss tangent tan δ obtained (hereinafter also referred to as “tan δ peak value”) is preferably 1.0 to 5.0, more preferably 1.5 to 5.0, and still more preferably 2.0 to 4. It is desirable to be in the range of 0.0.

  The 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention is further obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in a temperature range of −40 to 150 ° C. The temperature at which the value of the loss tangent tan δ is maximized (hereinafter also referred to as “tan δ peak temperature”) is preferably −10 to 40 ° C., more preferably 0 to 40 ° C.

<Method for producing 4-methyl-1-pentene / α-olefin copolymer (A)>
A method for producing the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention will be described.

  For the production of the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, a conventionally known catalyst such as a magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. The metallocene catalysts described in the pamphlet No. 01/27124, JP-A-3-193966 or JP-A-02-41303 are preferably used, and more preferably represented by the following general formula (1) or (2). An olefin polymerization catalyst containing a metallocene compound is preferably used.

(Wherein 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 are hydrogen, carbonized, Selected from a hydrogen group and a silicon-containing hydrocarbon group, which may be the same or different, and adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form a ring; R ⁵ to R ¹² Up to adjacent substituents may combine with each other to form a ring,
A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and A is two or more rings including a ring formed with Y May contain structure,
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 in the} 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 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. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position corresponds to the ^{R 7, R 10, R 6} , 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. 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, difluorophenylmethylene. Methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, dicyclohexyl Silylene, 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.

  Specific examples of the metallocene compound in the present invention include compounds exemplified in WO 01/27124, WO 2006/025540, or WO 2007/308607. In particular, this does not limit the scope of the present invention.

When using a metallocene compound for the production of the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, the catalyst component is:
(A) a metallocene compound (for example, a metallocene compound represented by the above general formula (1) or (2));
(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 compound selected from organoaluminum compounds;
If necessary,
(C) It is comprised from a particulate carrier. As a production method, for example, the method described in International Publication No. 01/27124 pamphlet 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.

  In the production of the 4-methyl-1-pentene / α-olefin copolymer (A) according to the present invention, 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 may be used. Specific examples of the inert hydrocarbon include aliphatic carbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrogen; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogens such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane And hydrocarbons, and mixtures thereof.

Bulk polymerization using 4-methyl-1-pentene and α-olefin itself as a solvent can also be carried out.
Further, 4-methyl-1-pentene having a controlled composition distribution was obtained by performing stepwise polymerization of 4-methyl-1-pentene and copolymerization of 4-methyl-1-pentene and α-olefin. It is also possible to obtain an α-olefin 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 is suitably about 0.001 to 100 NL per 1 kg of the total of 4-methyl-1-pentene and α-olefin. .

<Thermoplastic elastomer composition (B)>
The thermoplastic elastomer composition (B), which is one of the components contained in the thermoplastic polymer composition of the present invention, comprises an ethylene / α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II]. Is a composition obtained by dynamically crosslinking a mixture containing

<< Ethylene / α-Olefin / Nonconjugated Polyene Copolymer [I] >>
The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer [I], which is one of the components of the thermoplastic elastomer composition (B), is usually composed of (a) units derived from ethylene. (B) units derived from α-olefin are 50/50 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b) ] In the range of the molar ratio.

  The α-olefin constituting the ethylene / α-olefin / non-conjugated diene copolymer [I] according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, specifically, 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, 12-ethyl-1-tetradecene, and the like. Among these, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

Specific examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated diene copolymer [I] according to the present invention include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1 , 7-nonadiene, 4-ethylidene-1,7-undecadiene and the like chain non-conjugated dienes;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic nonconjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. A triene etc. are mentioned, These nonconjugated dienes can be used individually or in mixture of 2 or more types. Among these non-conjugated dienes, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable.

  The ethylene / α-olefin / nonconjugated polyene copolymer [I] according to the present invention usually has an iodine value of 1 to 50, preferably 5 to 40, more preferably 10 as an index of the amount of the nonconjugated polyene component. It is in the range of -30. The total amount of non-conjugated diene components is usually in the range of 2 to 20% by mass in the component [I].

  The ethylene / α-olefin / non-conjugated polyene copolymer [I] according to the present invention usually has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 1 to 10 dl / g, preferably 1.5. It is in the range of ~ 8 dl / g.

  The ethylene / α-olefin / non-conjugated polyene copolymer [I] according to the present invention 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 conventionally known mineral oil softeners such as paraffin process oil.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer [I] according to the present invention is usually in the range of 10 to 250, preferably 30 to 150.

  The ethylene / α-olefin / non-conjugated polyene copolymer [I] according to the present invention may be used alone or in combination of two or more ethylene / α-olefin / non-conjugated polyene copolymers.

The ethylene / α-olefin / non-conjugated polyene copolymer [I] according to the present invention can be produced by a conventionally known method.
<< Polyolefin resin [II] >>
Polyolefin resin [II] which is one of the components of the thermoplastic elastomer composition (B) according to the present invention includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, A homopolymer of α-olefin such as 1-octene and 1-decene, or a copolymer having two or more α-olefins and usually having a main α-olefin content of 90 mol% or more, and having a melting point ( Tm) is in the range of 70-200 ° C, preferably 80-170 ° C.

The polyolefin resin [II] according to the present invention usually has substantially no unsaturated bond in the main chain.
The polyolefin resin [II] according to the present invention may be used alone or in combination of two or more olefin polymers.

Among these polyolefin resins [II], propylene polymer (II-1) and ethylene polymer (II-2) are preferable.
<Propylene polymer (II-1)>
The propylene polymer (II-1) according to the present invention is a homopolymer of propylene, or propylene and usually an α-olefin having 2 to 10 carbon atoms of 10 mol% or less, such as ethylene, 1-butene, It is a random copolymer with 1-pentene, 4-methyl-1-pentene, or a block copolymer of a propylene homopolymer and an amorphous or low crystalline propylene / ethylene random copolymer. Usually, the melting point is in the range of 120 to 170 ° C, preferably 145 to 165 ° C.

The propylene polymer (II-1) according to the present invention is usually produced and sold as a polypropylene resin.
The propylene polymer (II-1) according to the present invention preferably has an isotactic structure as a steric structure, but a syndiotactic structure, a mixture of these structures, or a partly atactic structure. The inclusion can also be used.

  The propylene polymer (II-1) according to the present invention usually has a melt flow rate (measured at a temperature of 230 ° C. and a load of 21.18 N according to MFR: JIS K6758) of 0.05 to 100 g / 10 minutes, preferably It exists in the range of 0.1-50 g / 10min.

The propylene-based polymer (II-1) according to the present invention is polymerized by various known polymerization methods.
<Ethylene polymer (II-2)>
The ethylene polymer (II-2) according to the present invention is a homopolymer of ethylene or an α-olefin having 2 to 10 carbon atoms and less than 10 mol% of ethylene, for example, propylene, ethylene, 1-butene, It is a random copolymer with 1-pentene, 4-methyl-1-pentene and the like, and usually has a melting point of 80 to 150 ° C, preferably 90 to 130 ° C.

The ethylene polymer (II-2) according to the present invention is usually produced and sold as a high-pressure method low-density polyethylene, linear low-density polyethylene, high-density polyethylene, or the like.
The ethylene-based polymer (II-2) according to the present invention usually has a melt flow rate (measured in accordance with MFR: JIS K6758 at a temperature of 190 ° C. and a load of 21.18 N) of 0.05 to 100 g / 10 minutes, preferably It exists in the range of 0.1-50 g / 10min.

<Crosslinking agent>
Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds, phenolic vulcanizing agents such as phenol resins, etc. Among them, organic peroxides are preferably used.

  Specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-Di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Examples include carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

  Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 in terms of odor and scorch stability 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) ) Valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

  These organic peroxides are usually 0.01 to 15 parts by weight, preferably 100 parts by weight in total of ethylene / α-olefin / non-conjugated polyene copolymer [I] and polyolefin resin [II]. Is used in a ratio of 0.03 to 12 parts by mass. When the organic peroxide is used in the above ratio, a thermoplastic elastomer composition (B) in which at least a part of the ethylene / α-olefin / non-conjugated polyene copolymer [I] is crosslinked is obtained. A molded article having sufficient characteristics and rubber elasticity can be obtained.

<Crosslinking aid>
In the present invention, during the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine , Crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate A crosslinking aid comprising a polyfunctional methacrylate monomer such as allyl methacrylate, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate may be added. By adding such a crosslinking aid, uniform and mild crosslinking reaction of the ethylene / α-olefin / non-conjugated polyene copolymer [I] can be expected. In particular, when divinylbenzene is used in the present invention, it is easy to handle and compatible with the ethylene / α-olefin / non-conjugated polyene copolymer [I] and the polyolefin resin [II], which are the main components of the material to be treated. Is good, and has the solubilizing action of the organic peroxide, and acts as a dispersion aid for the organic peroxide, so the crosslinking effect by heat treatment is homogeneous, and the thermoplasticity has a good balance between fluidity and physical properties. Since an elastomer composition (B) is obtained, it is most preferable.

  The crosslinking aid according to the present invention is usually 0.01 to 15 parts by mass with respect to 100 parts by mass of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer [I] and the polyolefin resin [II]. , Preferably it is used in the ratio of 0.03-12 mass parts.

<Softener>
A softener may be added to the precursor according to the present invention as a fluidity or hardness adjusting agent during dynamic crosslinking.

  The softening agent is an ethylene / α-olefin / non-conjugated polyene copolymer [I], a polyolefin resin [II], or an ethylene / α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II]. It can be added at the time of mixing or by a method in which the mixture (precursor) is injected during dynamic crosslinking. In that case, you may add the said method individually or in combination of the said method.

Specific examples of the softener according to the present invention include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petroleum jelly; coal tar, coal tar pitch, and the like. Coal tar softener;
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil; tall oil; sub, (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid Fatty acids and fatty acid salts such as barium stearate, calcium stearate, zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene; Ester softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal modified polyisoprene, hydrogenated terminal modified polyisoprene, liquid thiocol, hydrocarbon-based compounds Such as lubricating oil, and the like. Among these, petroleum softeners, particularly process oils are preferably used.

  When the softening agent according to the present invention is added, the amount is usually 10 to 200 parts by weight, preferably 15 to 150 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer [I]. Preferably it mix | blends in the range of 20-80 mass parts. When the softener is used in the above ratio, the resulting thermoplastic elastomer composition (B) has excellent fluidity during molding and does not deteriorate the mechanical properties of the resulting molded article. In this invention, when the usage-amount of a softener exceeds 200 mass parts, it exists in the tendency for the heat resistance of the thermoplastic elastomer composition (B) obtained and heat aging resistance to fall.

<Other additives>
In the thermoplastic elastomer composition (B) of the present invention or the precursor, additives such as a slip agent, a nucleating agent, a filler, an antioxidant, a weathering stabilizer, a colorant, and a foaming agent are added as necessary. Can be blended as long as the object of the present invention is not impaired.

  Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents, and these can be used alone or in combination of two or more. Non-melting crystallization nucleating agents include inorganic substances such as talc, mica, silica, aluminum, brominated biphenyl ether, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), organophosphate, rosin crystallization Nucleating agents, substituted triethylene glycol terephthalate and Terylene & Nylon fibers, etc., especially hydroxy-di-p-tert-butylbenzoic acid aluminum salt, methylenebis (2,4-di-tert-butylphenyl) phosphoric acid sodium salt, 2, 2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, rosin-based crystallization nucleating agent is desirable. Examples of the melting crystallization nucleating agent include sorbitol-based compounds such as dibenzylidene sorbitol (DBS), substituted DBS, and lower alkyl dibenzylidene sorbitol (PDTS).

Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.
Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber, and the like.

<Method for producing thermoplastic elastomer composition (B)>
The thermoplastic elastomer composition (B) according to the present invention is a mixture containing ethylene / α-olefin / non-conjugated polyene copolymer [I] and polyolefin resin [II], preferably ethylene / α-olefin / non-conjugated. Mixture containing polyene copolymer [I] and polyolefin resin [II] in the range of [I] / [II] (mass ratio) of 90/10 to 5/95, more preferably 70/30 to 10/90 Alternatively, it can be obtained by dynamically cross-linking a mixture (precursor) containing a predetermined amount such as the softener as necessary. When dynamic crosslinking is performed, heat treatment is preferably performed dynamically in the presence of the crosslinking agent or in the presence of the crosslinking agent and the crosslinking aid.

Here, “dynamically heat-treating” means kneading in a molten state.
The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of heat processing is the range of 300 degreeC from melting | fusing point of an olefin type polymer (B), and is 150-270 degreeC normally, Preferably it is 170 degreeC-250 degreeC. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10～50,000Sec ^-1 shear rate, preferably in the range of 100~10,000sec ^-1.

  As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a uniaxial or biaxial extruder can be used, and a non-open type apparatus is preferable.

  According to the present invention, the thermoplastic elastomer composition (B) in which at least a part of the ethylene / α-olefin / non-conjugated polyene copolymer [I] is crosslinked is obtained by the dynamic heat treatment described above.

<Propylene polymer (C)>
The propylene polymer (C), which is one of the components contained in the thermoplastic polymer composition of the present invention, has a syndiotactic pentad fraction (hereinafter referred to as “rrrr fraction”) measured by ¹³ C-NMR. 85) or more, preferably 90% or more, more preferably 93% or more, and still more preferably 94% or more, and 90 to 100 mol%, preferably 92 to 100 mol, of structural units derived from propylene. %, More preferably 95 to 100 mol% of a propylene-based polymer.

  The propylene polymer (C) having an rrrr fraction in the above range is excellent in moldability, heat resistance and transparency, and has better properties as crystalline polypropylene.

The rrrr fraction of the propylene polymer (C) according to the present invention is measured as follows.
The rrrr fraction is expressed in terms of Prrrr (absorption intensity derived from the third unit methyl group at a site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (all methyl groups of propylene units) in the ¹³ C-NMR spectrum. (Absorption intensity derived from the above) is determined by the following formula (1).

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C * NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 8,000 times or more.

  The propylene-based polymer (C) according to the present invention is a homopolymer of propylene or an α-olefin having 2 to 20 carbon atoms of propylene and 10 mol% or less, such as ethylene, 1-butene, 1- It is a copolymer with pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. As the α-olefin copolymerized with propylene, ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. The α-olefin copolymerized with propylene may be one type or two or more types.

The propylene polymer (C) according to the present invention is preferably a propylene polymer having a heat of fusion (ΔH _C ) of 20 J / g or more, more preferably 40 J / g or more, and even more preferably 50 J / g or more. . The upper limit of the heat of fusion (ΔH _C ) is not particularly limited, but is usually 120 J / g or less.

  The propylene polymer (C) according to the present invention preferably has a melting point (Tm) obtained by differential scanning calorimetry (DSC) measurement of 145 ° C. or higher, more preferably 147 ° C. or higher, and further preferably 150 ° C. or higher. Particularly preferably, it is 155 ° C. or higher. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example. The propylene polymer (C) having a melting point (Tm) in the above range is excellent in moldability, heat resistance and mechanical properties.

  The propylene-based polymer (C) according to the present invention preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.5 to 10 dl / g, more preferably 1.0 to 6 dl / g, Desirably, it is preferably in the range of 1.0 to 4 dl / g, and when the intrinsic viscosity is in such a range, it exhibits good fluidity, is easily blended with other components, and the resulting thermoplastic polymer. The composition tends to obtain a molded article having excellent mechanical strength.

  The propylene polymer (C) according to the present invention is not particularly limited as long as the thermoplastic polymer composition obtained by blending the propylene polymer (C) can be molded. The MFR measured under a 2.16 kg load is in the range of 0.001 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min, more preferably 0.1 to 10 g / 10 min.

The propylene-based polymer (C) according to the present invention can be obtained by various known production methods such as the production method described in International Publication No. WO2006 / 123759.
<Propylene copolymer (D)>
The propylene copolymer (D), which is one of the components contained in the thermoplastic polymer composition of the present invention, has a propylene-derived constitutional unit in an amount of 40 to 89 mol%, preferably 50 to 89 mol%, more preferably. 55 to 89 mol%, 11 to 60 mol%, preferably 11 to 50 mol%, more preferably 11 to 45 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and the following (d1) It is a propylene-based copolymer satisfying the above.

  (D1) The intrinsic viscosity [η] (dl / g) measured at 135 ° C. and decalin and the MFR measured at 230 ° C. and a load of 2160 g are expressed by the following relational expression (2), preferably the following relational expression (3). Fulfill.

1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20) (2)
1.80 × MFR ^(−0.20) ≦ [η] ≦ 2.50 × MFR ^(−0.19) (3)
The propylene-based polymer (D) satisfying the formula (2), preferably the formula (3), of the above (d1) has a large MFR with the same intrinsic viscosity [η] as compared with the conventional isotactic propylene-based copolymer. Show.

  As described in Macromolecules 31, 1335-1340 (1998), the molecular weight between the entanglement points of isotactic polypropylene (reported as Me = 6900 (g / mol) in the paper) and the syndiotactic polypropylene This is thought to be due to the difference in molecular weight between entanglement points (reported as Me = 2170 (g / mol) in the paper). That is, it is considered that the same [η] has a syndiotactic structure, so that the number of entanglement points increases with respect to the material having the isotactic structure, and the MFR increases.

  As described above, (d1) the propylene polymer satisfying the above formula (2) is a polymer having stereoregularity different from that of the propylene polymer having an isotactic structure, and is so-called syndiotactic. It is considered to have a structure. In this case, the obtained thermoplastic polymer composition is excellent in wear resistance.

  The propylene copolymer (D) according to the present invention comprises propylene and an α-olefin having 2 to 20 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. As the α-olefin copolymerized with propylene, ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. The α-olefin copolymerized with propylene may be one type or two or more types.

  The propylene copolymer (D) according to the present invention is preferably a polymer having a melting point of less than 90 ° C., more preferably 80 ° C. or less, and still more preferably a melting point does not exist. In the present invention, the absence of melting point means that the heat of fusion ΔH due to the melting peak is 1 J / g or less.

  The propylene copolymer (D) according to the present invention is not particularly limited as long as the thermoplastic polymer composition obtained by mixing the propylene copolymer (D) can be processed. The MFR measured under a 2.16 kg load is 0.01 to 100 g / 10 min, preferably 0.01 to 50 g / 10 min, more preferably 0.1 to 30 g / 10 min, and particularly preferably 0.1 to 10 g. / 10 min.

  The propylene copolymer (D) according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g, more preferably It is desirable to be in the range of 0.1-5 dl / g. When the propylene copolymer (D) having an intrinsic viscosity [η] in the above range is used, the resulting thermoplastic polymer composition has excellent fluidity during molding and sufficient mechanical properties of the resulting molded article. is there.

  The propylene copolymer (D) according to the present invention usually has an Mw / Mn (polystyrene conversion) measured by GPC in the range of 1.2 to 3.5, more preferably 1.5 to 3.0.

The propylene copolymer (D) according to the present invention may be one in which the rr fraction measured by the ¹³ C-NMR method takes a value within a specific range, as shown below. Preferably, the rr fraction is 40% or more, more preferably 45% or more.
The rr fraction is defined as Prr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the second unit at a site where three units of the propylene unit are continuously syndiotactically bonded) and Pw (total methyl group of the propylene unit). (Absorption intensity derived from the above) is determined by the following formula (4).

rr fraction (%) = 100 × Prr / Pw (4)
Here, mr-derived absorption (absorption derived from at least both syndiotactic bonds and isotactic bonds among three propylene units, used for determination of Pmr (absorption intensity)), rr-derived absorption (propylene Absorption derived from the methyl group of the second unit at the site where three units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or absorption derived from mm (three consecutive units of propylene units) If the absorption derived from the methyl group of the second unit at the isotactic bond site and Pmm (absorption intensity) overlap with the absorption derived from the comonomer, the contribution of the comonomer component is subtracted. Calculate as it is.

  Specifically, among the description of how to obtain the “syndiotacticity parameter (SP value)” described in JP-A-2002-097325 from [0018] to [0031], [0018] to [0023] ] Is calculated by the above formula (4) from the integrated intensity of the signals in the first region, the second region, and the third region.

In the measurement of the rr value, the NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-400 NMR measurement apparatus manufactured by JEOL. The number of integration is 8,000 times or more.
The rr value is an index indicating that the propylene copolymer (D) has a higher proportion of so-called syndiotactic structures.

  When the propylene copolymer (D) according to the present invention satisfies the condition (d1), the structural unit derived from propylene is, for example, 40 to 89 mol%, preferably 50 to 89 mol%, more preferably 55 to 80 mol%, The structural unit derived from ethylene is, for example, 1 to 35 mol%, preferably 1 to 30 mol%, more preferably 5 to 20 mol%, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is, for example, 10 to 45 mol. %, Preferably 10 to 40 mol%, more preferably 15 to 40 mol% of propylene / ethylene / C4-20 α-olefin copolymer (D1) is desirable. In this case, the total amount of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from α-olefin having 4 to 20 carbon atoms in the content of the structural unit derived from α-olefin having 4 to 20 carbon atoms. The total amount of propylene-derived structural units, ethylene-derived structural units, and α-olefin-derived structural units having 4 to 20 carbon atoms in proportion (mol%) (Pb2-2) to ethylene The ratio (mol%) to (Pb2-1) preferably satisfies the relationship Pb2-2> Pb2-1, and P (b2-2) -P (b2-1) ≧ 1 mol% or more. More preferred.

In the case where the propylene copolymer (D) according to the present invention satisfies the condition (c1), in addition to the propylene / ethylene / α-olefin copolymer (D _I ), for example, 50 to 50 structural units derived from propylene are used. 89 mol%, preferably 55 to 89 mol%, more preferably 65 to 85 mol%, and ethylene-derived structural units such as 11 to 50 mol%, preferably 11 to 45 mol%, more preferably 15 to 35 mol% Mention may also be made of propylene / ethylene copolymers (D _II ). When (D _I ) and (D _II ) are compared, propylene / ethylene / α-olefin copolymer (D _I ) is preferred.

  The propylene copolymer (D) according to the present invention can be produced by various known production methods. For example, it can be obtained by copolymerizing propylene and α-olefin with a catalyst capable of producing syndiotactic propylene. More specifically, for example, it can be produced by the method of International Publication No. 2008-059895, but is not limited thereto.

<Thermoplastic polymer composition>
In one embodiment of the thermoplastic polymer composition of the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B) are combined into (A) / ( B) A thermoplastic polymer composition containing (mass ratio) in the range of 10/90 to 49/51, preferably 10/90 to 45/55, and more preferably 15/85 to 45/55.

  The thermoplastic polymer composition of the present invention comprises a 4-methyl-1-pentene / α-olefin copolymer (A) and a thermoplastic elastomer composition (B) in the above range, thereby providing flexibility and texture. And the touch can be improved.

In the thermoplastic polymer composition of the present invention, in addition to the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B), other components are used in the present invention. The composition may be included so long as it does not impair the purpose. The first composition of the present invention usually has a sea-island structure in which the component (A) is dispersed in the component (B). This is thought to lead to good flexibility, less crease, good texture and feel.

In another aspect of the thermoplastic polymer composition of the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A), the thermoplastic elastomer composition (B), and the propylene polymer are used. (C) and the propylene copolymer (D), a 4-methyl-1-pentene / α-olefin copolymer (A) and a thermoplastic elastomer composition (B) the propylene polymer. Mass ratio [(A) / [(B) + (C) + (D)] with the total amount [(B) + (C) + (D)] with (C) and the propylene copolymer (D) ] Is 10/90 to 49/51, preferably 10/90 to 45/55, more preferably 10/90 to 43/57, and [(C) + (D)] / [(A) + (B)] is 0 to 100/100 (mass ratio), preferably 0 to 80/100 (quality) (C) / (D) is in the range of 5/95 to 90/10 (mass ratio), preferably in the range of 10/90 to 80/20 (mass ratio).

  The thermoplastic polymer composition of the present invention comprises the propylene polymer (C) in addition to the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B). By including the propylene copolymer (D), the wear resistance and scratch resistance are improved.

  The thermoplastic polymer composition of the present invention includes the 4-methyl-1-pentene / α-olefin copolymer (A), the thermoplastic elastomer composition (B), the propylene-based polymer (C), and the In addition to the propylene copolymer (D), a composition containing other components as long as the object of the present invention is not impaired may be used.

  Other components include various weathering stabilizers, heat stabilizers, antioxidants, UV absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, and aging. Inhibitors, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, flame retardants, and other polymers (E) Can be mentioned. The other polymer (E) is not particularly limited, but a polymer that does not satisfy any of the above requirements (A), (B), (C), and (D), such as a thermoplastic resin and an elastomer. Etc. The second composition of the present invention usually has a sea-island structure in which component (A) is present as a dispersed phase. This is considered to lead to good flexibility, resistance to wrinkling, good texture and touch, and to the development of wear resistance.

<Method for producing thermoplastic polymer composition>
The thermoplastic polymer composition of the present invention can be produced by various known methods. For example, the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B), and further the thermoplastic polymer composition comprises the propylene polymer (C) and When the propylene copolymer (D) is contained, it is obtained by a method of mechanically mixing each component within a predetermined range by various known methods, or a method of mixing and then melt-kneading using an extruder. It is done.

Here, 4-methyl-1-pentene / α-olefin copolymer (A), propylene-based polymer (C), and propylene copolymer (D) produce the thermoplastic polymer composition of the present invention. You may mix at arbitrary timings. For example, after obtaining a thermoplastic elastomer composition (B), a 4-methyl-1-pentene / α-olefin copolymer (A), a thermoplastic elastomer composition (B), and a propylene-based polymer (C) The propylene copolymer (D) may be mixed, or 4-methyl-1-pentene / α- during mixing of the ethylene / α-olefin / non-conjugated polyene copolymer [I] and the polyolefin resin [II]. The olefin copolymer (A), the propylene polymer (C), and the propylene copolymer (D) may be mixed together.

<Uses of thermoplastic polymer composition>
The thermoplastic polymer composition of the present invention can be formed by various known molding methods, specifically, thermoplastic elastomer molding by various molding methods such as extrusion molding, press molding, injection molding, calendar molding, and hollow molding. It can be a body. Furthermore, a molded body such as a sheet obtained by the above molding method can be formed into a molded body by secondary processing by thermoforming or the like, or laminated with other materials.

  Examples of the base material that can be laminated include cloth, resin, rubber, and wood. Specifically, the fabric includes cotton, hemp, wool, rayon, polyester, nylon, vinylon, polypropylene, polyethylene, acrylic, aramid, carbon-based woven fabric, knitted fabric, nonwoven fabric, and the like. As the resin, a thermoplastic resin and a thermosetting resin, and as the rubber, a film or sheet such as a thermoplastic elastomer or a thermosetting elastomer (vulcanized rubber) is preferable. Lamination is usually carried out via an adhesive, but in the case of lamination with polyethylene or polypropylene, lamination by thermal fusion is possible without using an adhesive.

  The thermoplastic polymer composition according to the present invention is not particularly limited in its use, but for example, automotive parts, civil engineering / building materials, electrical / electronic parts, sanitary goods, films / sheets, foams, It is suitable for various known uses such as artificial leather, and particularly suitable for automobile parts such as automobile interior materials and skin materials such as artificial leather.

<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 Channels, instrument panel skins, door skins, ceiling skins, weatherstrip materials, hoses, steering wheels, boots, wire harness covers, seat adjuster covers, etc. can be exemplified, among which the thermoplastic polymer composition of the present invention has a texture. It is particularly preferable because it can improve the touch and feel.

<Civil engineering / building materials>
Civil engineering and building materials that can be used in the molded thermoplastic polymer composition of the present invention include, for example, ground improvement sheets, waterworks, noise prevention walls and other civil engineering materials and construction materials, civil engineering and architectural gaskets, and Sheets, water-stopping materials, joint materials, window frames for construction, and the like can be exemplified, and among them, the thermoplastic polymer composition of the present invention is particularly preferable because it can improve the texture and feel.

<Electric / electronic parts>
Examples of the electric / electronic parts that can be used in the molded thermoplastic polymer composition of the present invention include electric / electronic parts such as wire coating materials, connectors, caps, and plugs. The plastic polymer composition is particularly preferable because it can improve the texture and feel.

<Hygiene products>
Examples of the sanitary product that can be used for the molded article of the thermoplastic polymer composition of the present invention include sanitary products such as sanitary products, disposable diapers, and grips for toothbrushes, among others, the thermoplastic polymer composition of the present invention. The thing is particularly preferable because it can improve the texture and feel.

<Film / Sheet>
Examples of films and sheets that can be used for the thermoplastic polymer composition molded article of the present invention include, for example, infusion bags, medical containers, automotive interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort containers, A pipe, a transparent substrate, a sealant and the like can be exemplified, and among them, the thermoplastic polymer composition of the present invention is particularly preferable because it can improve the texture and feel.

<Artificial leather>
Examples of the artificial leather that can be used for the thermoplastic polymer composition molded article of the present invention include, for example, chair skins, bags, school bags, athletics shoes and marathon shoes, sports shoes such as running shoes, jumpers, coats, Such as wear, belt, bag, ribbon, notebook cover, book cover, key holder, pen case, wallet, business card holder, periodic case, etc.In particular, the thermoplastic polymer composition of the present invention has a texture and texture on leather. This is particularly preferable because the touch feeling can be improved.

<Method for producing coated molded body>
Usually, when a skin material made of a thermoplastic polymer composition is attached to the surface of a base material, the skin material is often softened by heating, so the skin material is often deformed to wave, In this way, there is a problem that a large number of wrinkles may occur in the pasted skin material when trying to paste the undulating skin material on the base material.

However, the skin material comprising the thermoplastic polymer composition of the present invention has a feature that it is difficult to wrinkle when it is attached to a substrate.
As a method of coating the base material with the skin material comprising the thermoplastic polymer composition of the present invention, specifically, for example, after applying an adhesive to the surface of the base material obtained in advance or drying it. Thereafter, a skin material made of the thermoplastic polymer composition is applied onto the surface of the base material by using a method of coating the skin material made of the thermoplastic polymer composition by pressure bonding, thermoforming such as vacuum or air pressure molding. Various known coatings such as a coating method, a method of covering a base material after spreading a skin material made of a thermoplastic polymer composition, and a method of attaching a skin material made of a thermoplastic polymer composition during molding of the base material You can take a method.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.
[Measurement conditions]
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% by volume) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (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, 27.50 ppm as standard for chemical shift Measured as a value.

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

[Melting point (Tm)]
The melting point (Tm) of the polymer 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).

[Intrinsic viscosity]
The intrinsic viscosity [η] of the polymer was measured at 135 ° C. using a decalin solvent.
[Molecular weight (Mw, Mn), molecular weight distribution (Mw / Mn)]
The molecular weight of the polymer is liquid chromatograph: Waters ALC / GPC 150-C plus type (with suggested refractometer detector integrated type), and Tosoh Corporation GMH6-HT × 2 and GMH6-HTL × 2 as columns. The books were connected in series, and o-dichlorobenzene was used as the mobile phase medium, and the flow rate was 1.0 ml / min and measurement was performed at 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.

[Sheet molding]
Resin pellets from raw material supply hoppers connected to the surface layer (A), base material layer (C), and adhesive layer (B) using a T-die molding machine having a die width of 200 mm, which is also equipped with a 30 mmφ single screw extruder The raw material pellets were melted through a cylinder in a single-screw extruder, and extrusion molding was performed from a T-die to obtain a sheet having a total thickness of 500 μm.

[Shore A hardness]
In the measurement of Shore A hardness (based on JIS K6253), a press sheet having a thickness of 3 mm was used as a measurement sample, and the graduations were read immediately after the start of pressing contact and 15 seconds after the start of pressing contact.

(Dynamic viscoelasticity)
A press sheet having a thickness of 3 mm was prepared using the composition, and a strip of 45 mm × 10 mm × 3 mm necessary for dynamic viscoelasticity measurement was cut out. The temperature dependence of dynamic viscoelasticity from −40 to 150 ° C. was measured at a frequency of 10 rad / s using MCR301 manufactured by ANTONPaar, and the loss tangent (tan δ) due to the glass transition temperature in the range of 0 to 30 ° C. ) At the peak value (maximum value) (hereinafter also referred to as “peak temperature”), and the value of the loss tangent (tan δ) at that time.

(Stress relaxation measurement)
A sample punched out from a 500 μm sheet into a sheet having a length of 100 mm and a width of 10 mm was used, and a test piece was stretched by 10% at a tensile speed of 200 mm / min using an Instron universal tensile tester 3380. 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.

[Feeling (sensory evaluation)]
A total of 10 men and women from 20 to 50 years old were collected as subjects. Each test subject was allowed to enter an environmental test chamber conditioned at 23 ° C. and 50% RH and rested for a while, and then the sheet of the example or comparative example was stroked with a finger. An interview survey was conducted on the tactile sensation at that time, and the following five levels were evaluated.

In addition, the tactile sensation was considered to be excellent when it had a moist and smooth feeling. Therefore, the determination was made based on the degree of lack of moist or smooth feeling.
5: Tactile feel is excellent.
4: Tactile feeling is slightly better.
3: Normal.
2: Tactile feeling is slightly inferior.
1: Tactile feel is inferior.
[Formability]
Using a 500 μm sheet, a sheet heated to 100 to 130 ° C. with a hot air dryer is stretched by about 150%, and then a homo PP plate (a plate obtained by injection molding a propylene homopolymer) (an injection molding machine) ) With a mold of 120 × 120 × 2 mmt) in the manner of hot stamping molding. The molded product was observed visually, and the moldability was evaluated in the following three stages.

○: No wrinkles or the like.
Δ: Almost no wrinkles.
X: Wrinkles etc. occurred.

[Polymerization example of 4-methyl-1-pentene / α-olefin copolymer (A)]
[Polymerization Example 1]
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 was 36.9 g, and the 4-methyl-1-pentene content in the polymer was 72.5 mol% and the propylene content was 27.5 mol%.

[Polymerization Example 2]
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 30 ° C., pressurized with propylene so that the total pressure became 0.74 MPaG, and 12 Nml of hydrogen was added. Subsequently, methylaluminoxane prepared in advance, 1 mmol in terms of Al, diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) A toluene solution containing 0.35 ml of zirconium dichloride in an amount of 0.005 mmol was pressed into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 60 ° C. for 60 minutes. 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 resulting rubbery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 56.3 g, the 4-methyl-1-pentene content in the polymer was 24.7 mol%, and the propylene content was 75.3 mol%.

[Polymerization Example 3]
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen was charged with 300 ml of normal hexane at 23 ° C. (dried in a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene. . 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 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride into the autoclave with nitrogen. 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 was 44.0 g, and the 4-methyl-1-pentene content in the polymer was 84.1 mol% and the propylene content was 15.9 mol%. Table 1 shows the measurement results of various physical properties.

[Thermoplastic elastomer composition (B)]
The following thermoplastic elastomer composition was used as the thermoplastic elastomer composition (B).
Made by Mitsui Chemicals, 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 min.

  Made by Mitsui Chemicals, Inc., 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 min.

[Propylene polymer (C)]
<Propylene polymer (C-1)>
The propylene polymer (C-1) used was synthesized as follows.

To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with sufficient nitrogen substitution, to which was added 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), followed by dibenzylmethylene (cyclopentadiene). Toluene solution (5.0 μmol) of (enyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. under normal pressure for 45 minutes, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.38 g of a polymer was obtained. The polymerization activity is 0.63 kg-PP / mmol-Zr · hr, and the resulting propylene homopolymer (A-1) has an ultimate fineness [η] of 1.9 dl / g, Tm = 158 ° C. (Tm1 = 152). C, Tm2 = 158 ° C.), the pentad fraction (rrrr fraction) was 93.5%, the heat of fusion (ΔH _C ) was 57 J / g, and Mw / Mn = 2.0. .

[Propylene copolymer (D)]
<Propylene copolymer (D-1)>
Into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 833 ml of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, then the temperature inside the polymerization apparatus was raised to 60 ° C. and propylene was used. After the pressure in the system was increased to 0.33 MPa, the system pressure was adjusted to 0.63 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) are converted into aluminum. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.63 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, a polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained propylene / ethylene / 1-butene copolymer (B-1) was 97 g, and the ultimate fineness [η] = 2.3 (dl / g) measured in 135 ° C. decalin. MFR (JIS K6721, 230 ° C., 2.16 kg load) was 1.3 g / 10 min. That is, the value on the left side of the expression (1) (condition (b4)) is 1.50 × (1.3) ^(−0.20) = 1.42, and the value on the right side is 2.65 × (1.3) ^{( -0.20)} = 2.51, which ^shows that the expression (1) is satisfied.

The glass transition point obtained from DSC was −23.8 ° C., and the heat of fusion (ΔH _B ) was 1 J / g or less.
The composition of the propylene copolymer (D-1) was 62 mol% of the structural unit derived from propylene, 10 mol% of the structural unit derived from ethylene, and 28 mol% of the structural unit derived from 1-butene.

[Example 1]
4-Methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 10 parts by mass and Miralastomer 8030NHS: 90 parts by mass were mixed to obtain a thermoplastic polymer composition (Composition 1). . This composition 1: n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer as a secondary antioxidant with respect to 100 parts by mass Was blended in an amount of 0.2 parts by mass. Thereafter, using a twin screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd., under the conditions of a set temperature of 250 ° C., a resin extrusion amount of 60 g / min and 200 rpm. It was granulated and pelletized, and this was formed into a sheet and the physical properties were measured. Various physical properties are shown in Table 2-1.

[Example 2]
Instead of the composition 1 used in Example 1, obtained by mixing 25 parts by mass of 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1 and 75 parts by mass of Miralastomer 8030NHS. A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 2) was used. Various physical properties are shown in Table 2-1.

Example 3
In place of the composition 1 used in Example 1, the 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 40 parts by mass and Miralastomer 8030NHS: 60 parts by mass are mixed. A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 3) was used. Various physical properties are shown in Table 2-1.

Example 4
Instead of the composition 1 used in Example 1, the 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 10 parts by mass and Miralastomer 5030NHS: 90 parts by mass are mixed. A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 4) was used. Various physical properties are shown in Table 2-1.

Example 5
Instead of the composition 1 used in Example 1, 25 parts by mass of 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1 and 75 parts by mass of Miralastomer 5030NHS were obtained. A measurement sample was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 5) was used. Various physical properties are shown in Table 2-1.

Example 6
Instead of the composition 1 used in Example 1, 40 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1 and 60 parts by mass of Miralastomer 5030NHS were mixed. A measurement sample was prepared in the same manner as in Example 1 except that the obtained thermoplastic polymer composition (Composition 6) was used. Various physical properties are shown in Table 2-1.

Example 7
Instead of the composition 1 used in Example 1, 40 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 3 and 60 parts by mass of Miralastomer 8030NHS were mixed. A measurement sample was prepared in the same manner as in Example 1 except that the obtained thermoplastic polymer composition (Composition 7) was used. Various physical properties are shown in Table 2-1.

Example 8
Instead of the composition 1 used in Example 1, 40 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 3 and 60 parts by mass of Miralastomer 5030NHS were mixed. A measurement sample was prepared in the same manner as in Example 1 except that the obtained thermoplastic polymer composition (Composition 8) was used. Various physical properties are shown in Table 2-1.

Example 9
Instead of the composition 1 used in Example 1, 30 parts by mass / 10 mass parts of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1 and Polymerization Example 3, and Miralastomer 5030NHS: A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 9) obtained by mixing 60 parts by mass was used. Various physical properties are shown in Table 2-1.

[Comparative Example 1]
In place of the composition 1 used in Example 1, Miralastomer 8030NHS was used alone to form a sheet to prepare a measurement sample. Various physical properties are shown in Table 2-2.

[Comparative Example 2]
Instead of the composition 1 used in Example 1, the 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 75 parts by mass and Miralastomer 5030NHS: 25 parts by mass are mixed. A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition was used. Various physical properties are shown in Table 2-2.

[Comparative Example 3]
Instead of the composition 1 used in Example 1, 40 parts by mass of 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 2 and 60 parts by mass of Miralastomer 5030NHS were obtained. A measurement sample was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition was used. Various physical properties are shown in Table 2-2.

[Comparative Example 4]
Instead of the composition 1 used in Example 1, Miralastomer 8030NHS: 75 parts by mass and, as the other polymer (E), SIS [trade name Hybler 5127 manufactured by Kuraray Co., Ltd.]: 25 parts by mass are obtained. A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition was used. Various physical properties are shown in Table 2-2.

[Comparative Example 5]
In place of Composition 1 used in Example 1, Miralastomer 8030NHS: 75 parts by mass, and other polymer (E), hydrogenated styrene-based thermoplastic elastomer manufactured by Asahi Kasei Co., Ltd. Product name S.O.E L605: A sample for measurement was prepared in the same manner as in Example 1 except that a thermoplastic polymer composition obtained by mixing 25 parts by mass was used. Various physical properties are shown in Table 2-2.

Example 10
Instead of the composition 1 used in Example 1, 25 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1, 65 parts by mass of Miralastomer 8030NHS, propylene-based polymer ( Propylene polymer (C-1): 1.5 parts by mass as C) and propylene copolymer (D-1): 8.5 parts by mass as propylene polymer (D) A measurement sample was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 10) was used. Various physical properties are shown in Table 3.

Example 11
Instead of the composition 1 used in Example 1, 30 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1, 55 parts by mass of Miralastomer 5030NHS, propylene-based polymer ( Except for using a thermoplastic polymer composition (composition 11) obtained by mixing C-1): 2.3 parts by mass and propylene copolymer (D-1): 12.7 parts by mass. A measurement sample was prepared by performing the same operation as in Example 1. Various physical properties are shown in Table 3.

Example 12
Instead of the composition 1 used in Example 1, 30 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1, 50 parts by mass of Miralastomer 8030NHS, propylene-based polymer ( Example 1 except that a thermoplastic polymer composition (composition 16) obtained by mixing C-1): 3 parts by mass and propylene copolymer (D-1): 17 parts by mass was used. A measurement sample was prepared by performing the same operation. Various physical properties are shown in Table 3.

Example 13
Instead of the composition 1 used in Example 1, 25 parts by mass of 4-methyl-1-pentene / α-olefin copolymer obtained in Polymerization Example 1, 25 parts by mass of Miralastomer 8030NHS, propylene-based polymer ( C-1): 7 parts by mass, and propylene copolymer (D-1): 38 parts by mass, Asahi Kasei Co., Ltd. Tuftec H1221: 5 parts by mass obtained as a thermoplastic polymer A measurement sample was prepared in the same manner as in Example 1 except that the combined composition (Composition 17) was used. Various physical properties are shown in Table 3.

Claims (13)

Structural unit (i) derived from 4-methyl-1-pentene: 63 to 86 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene -Structural unit derived from olefin (ii): 14 to 37 mol% and structural unit derived from non-conjugated polyene (iii) 0 to 10 mol% [provided that structural units (i), (ii) and ( iii) 100 mol% in total] 4-methyl-1-pentene / α-olefin copolymer (A), and ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer [ I] and a thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing polyolefin resin [II],
A thermoplastic polymer composition, wherein the mass ratio (A) / (B) of the copolymer (A) and the composition (B) is from 10/90 to 49/51. Structural unit (i) derived from 4-methyl-1-pentene: 63 to 86 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene -Structural unit derived from olefin (ii): 14 to 37 mol% and structural unit derived from non-conjugated polyene (iii) 0 to 10 mol% (provided that structural units (i), (ii) and ( iii) a total of 100 mol%) 4-methyl-1-pentene / α-olefin copolymer (A),
A thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture containing an ethylene / carbon atom α-olefin / non-conjugated polyene copolymer [I] and a polyolefin resin [II],
A propylene-based polymer (C) having a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more and 90 to 100 mol% of a structural unit derived from propylene, and ,
Intrinsic viscosity [η] measured in decalin at 135 ° C. containing propylene-derived constitutional units in an amount of 40 to 89 mol% and carbon number 2 to 20 α-olefin-derived constitutional units in an amount of 11 to 60 mol%. MFR measured at (dl / g), 230 ° C., and load of 2160 g is the following relational expression: 1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20)
And a propylene copolymer (D) satisfying
The mass ratio (A) / [(B) + (C) + (D)] of the copolymer (A) and the composition (B) + polymer (C) + copolymer (D) is 10/90. A thermoplastic polymer composition characterized by being -49/51.   4-methyl-1-pentene / α-olefin copolymer (A) is a structural unit (i) derived from 4-methyl-1-pentene: 63 to 80 mol%, excluding 4-methyl-1-pentene Structural units derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms (ii): 20 to 37 mol% and structural units derived from non-conjugated polyenes (iii) 0 to 10 Or a 4-methyl-1-pentene / α-olefin copolymer, wherein the total of the structural units (i), (ii) and (iii) is 100 mol%), 2. The thermoplastic polymer composition according to 2.   The heat according to any one of claims 1 to 3, wherein the 4-methyl-1-pentene / α-olefin copolymer (A) has a melting point of less than 135 ° C. Plastic polymer composition.   The thermoplastic polymer according to claim 1 or 2, wherein the 4-methyl-1-pentene / α-olefin copolymer (A) has no melting point or less than 110 ° C. Composition.   The thermoplastic polymer composition according to any one of claims 1 to 5, wherein a tan δ peak is observed between 10 ° C and 40 ° C in the thermoplastic polymer composition.   The molded object obtained from the thermoplastic polymer composition of any one of Claims 1-6.   A skin material obtained from the thermoplastic polymer composition according to any one of claims 1 to 6.   A laminate having at least a part of the skin material according to claim 8.   An article coated with the skin material according to claim 8.   An automobile part coated with the skin material according to claim 8.   The manufacturing method of the molded object characterized by including the process of coat | covering a base material with the skin material of Claim 8.   The molded object obtained with the manufacturing method of Claim 12.