JP2014210869A - Thermoplastic polymer composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polymer composition suitable for obtaining a skin material which has excellent stress relaxation property (shape followability) and flexibility, hardly causes wrinkles when attaching a substrate and has a good tactile feeling.SOLUTION: There is provided a thermoplastic polymer composition which comprises: a 4-methyl-1-pentene-α-olefin copolymer (A) which contains (i) a constitutional unit derived from 4-methyl-1-pentene, (ii) a constitutional unit derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene and (iii) a constitutional unit derived from a non-conjugated polyene in a specific amount; and a thermoplastic elastomer composition (B) obtained by dynamically crosslinking a mixture comprising an ethylene-α-olefin having 3 to 20 carbon atoms-non-conjugated polyene copolymer [I] and a polyolefin resin [II], where the mass ratio (A)/(B) between the copolymer (A) and the composition (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.

  Conventionally, soft vinyl chloride resin has been the mainstream for interior skin materials such as instrument panels and door trims for automobiles, but in recent years, olefinic 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.

  Methods for improving stamping moldability include, for example, polyolefin resin (A), ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin / non-conjugated polyene copolymer rubber (B), and propylene / ethylene copolymer 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 80 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: 20 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.

  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): Derived from 63 to 80 mol%, preferably 65 to 75 mol%, at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. Structural unit (ii): 20 to 37 mol%, preferably 25 to 35 mol%, and structural unit (iii) derived from non-conjugated polyene 0 to 10 mol%, preferably 0 to 5 mol% (provided that , The sum 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 polymer (A) may contain 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.
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 (not observed). Or when it has melting | fusing 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.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、水素、炭化水素基およびケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ¹からＲ⁴までの隣接した置換基は互いに結合して環を形成してもよく、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成してもよく、
Ａは一部不飽和結合および／または芳香族環を含んでいてもよい炭素原子数２〜２０の２価の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、
Ｍは周期表第４族から選ばれた金属であり、
Ｙは炭素またはケイ素であり、
Ｑはハロゲン、炭化水素基、およびアニオン配位子または孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
ｊは１〜４の整数である。）

(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 / α-olefin / non-conjugated polyene copolymer [I], which is one of the components of the thermoplastic elastomer composition (B), is usually composed of (a) a unit derived from ethylene and (b) an α-olefin. To a molar ratio range of 50/50 to 95/5, preferably 60/40 to 80/20, and more preferably 65/35 to 75/25 [(a) / (b)]. is there.

  The α-olefin constituting the ethylene / α-olefin / non-conjugated diene copolymer rubber [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- Examples include pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. 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 rubber [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- Chain non-conjugated dienes such as 1,7-nonadiene, 4-ethylidene-1,7-undecadiene;
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 / non-conjugated polyene copolymer rubber [I] according to the present invention usually has an iodine value of 1 to 50, preferably 5 to 40, more preferably an index of the amount of the non-conjugated polyene component. It is in the range of 10-30. 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 rubber [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. It is in the range of 5-8 dl / g.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A1) according to the present invention may be a so-called oil-extended rubber in which a softening agent, preferably a mineral oil softening agent, is blended in 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 rubber [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 rubber [I] according to the present invention may be used alone or in combination of two or more types of ethylene / α-olefin / non-conjugated polyene copolymer rubber.
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) 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 mass with respect to 100 parts by mass of the total amount of ethylene / α-olefin / non-conjugated polyene copolymer rubber [I] and polyolefin resin [II]. Preferably it 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 rubber [I] is crosslinked is obtained. A molded article having sufficient tensile properties 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 rubber [I] can be expected. In particular, when divinylbenzene is used in the present invention, it is easy to handle and is compatible with the ethylene / α-olefin / non-conjugated polyene copolymer rubber [I] and the polyolefin resin [II], which are the main components of the object to be treated. It has good solubility, solubilization action of the organic peroxide, and works as a dispersion aid for the organic peroxide, so that the crosslinking effect by heat treatment is uniform, and the heat balances between fluidity and physical properties. Since a plastic elastomer composition (B) is obtained, it is the most preferable.

  The crosslinking aid according to the present invention is usually 0.01 to 15 masses per 100 mass parts of the total amount of ethylene / α-olefin / non-conjugated polyene copolymer rubber [I] and polyolefin resin [II]. Parts, preferably 0.03 to 12 parts by weight.

<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 may be ethylene / α-olefin / non-conjugated polyene copolymer rubber [I], polyolefin resin [II], or ethylene / α-olefin / non-conjugated polyene copolymer rubber [I] and polyolefin resin [II]. ] Or by mixing the mixture (precursor) 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 softener 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 / non-conjugated polyene copolymer rubber [I]. More preferably, it mix | blends in 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.

<Thermoplastic polymer composition>
The thermoplastic polymer composition of the present invention comprises (A) / (B) (mass ratio) of the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B). ) Is 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 addition to the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B), the thermoplastic polymer composition of the present invention includes other components as other components. The composition which contains a polymer and various additives in the range which does not impair the objective of this invention may be sufficient.

  Other polymers include, for example, thermoplastic resins, among which olefin polymers and styrene elastomers. These polymers may be used alone or in combination of two or more.

  Various additives used as other ingredients include various weather stabilizers, heat stabilizers, antioxidants, UV absorbers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, Pigments, dyes, anti-aging agents, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, co-crosslinking agents, cross-linking aids, adhesives, softeners, flame retardants, etc. .

<Method for producing thermoplastic polymer composition>
The thermoplastic polymer composition of the present invention can be produced by various known methods. For example, a method in which the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B) are mechanically mixed within a predetermined range by various known methods, or mixing Then, it is obtained by a method of melt kneading using an extruder.

  Here, the 4-methyl-1-pentene / α-olefin copolymer (A) may be mixed at an arbitrary timing for producing the thermoplastic polymer composition of the present invention. For example, after obtaining the thermoplastic elastomer composition (B), it may be mixed with 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic elastomer composition (B), or ethylene. The 4-methyl-1-pentene / α-olefin copolymer (A) may be mixed together when the α-olefin / non-conjugated polyene copolymer [I] and the polyolefin resin [II] are mixed.

<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 A sheet, a water-stopping material, a joint material, an architectural window frame, 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.

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 (differential 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]
Raw material pellets from a raw material supply hopper connected to the surface layer (A), the base material layer (C), and the adhesive layer (B) using a T-die molding machine having a die width of 200 mm, which also has 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 loss tangent (tan δ) due to 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 homo PP plate (molded with an injection molding machine with a 120 × 120 × 2 mmt mold) Affixed 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.

[Synthesis 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%.

[Comparative 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 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%.

[Thermoplastic elastomer composition (B)]
The following composition was used for 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.

[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.

[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.

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.

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.

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.

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.

[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.

[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 (Composition 7) was used. Various physical properties are shown in Table 2.

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

[Comparative Example 4]
Instead of the composition 1 used in Example 1, Miralastomer 8030NHS: 75 parts by mass and SIS [trade name Hibler 5127 manufactured by Kuraray Co., Ltd.]: 25 parts by mass are obtained as a thermoplastic polymer composition (composition) A measurement sample was prepared in the same manner as in Example 1 except that the product 9) was used. Various physical properties are shown in Table 2.

[Comparative Example 5]
It replaced with the composition 1 used in Example 1, and obtained by mixing Miralastomer 8030NHS: 75 mass parts and Asahi Kasei Co., Ltd. hydrogenated styrene-type thermoplastic elastomer brand name S.O.L L605: 25 mass parts. 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 2.

Claims (6)

Structural unit (i) derived from 4-methyl-1-pentene: 63-80 mol%, at least one α selected from α-olefins having 2-20 carbon atoms excluding 4-methyl-1-pentene -Structural unit derived from olefin (ii): 20 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]. Including
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.   A molded product obtained from the thermoplastic polymer composition according to claim 1.   A skin material obtained from the thermoplastic polymer composition according to claim 1.   A laminate having at least a portion of the skin material according to claim 3.   An article coated with the skin material according to claim 3.   An automobile part coated with the skin material according to claim 3.