JP2014214227A - Thermoplastic polymer composition and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polymer composition having excellent stress relaxation properties (shape followability) and flexibility, hard to be wrinkled upon application on a base material and suitable for obtaining a skin material having a satisfactory feeling.SOLUTION: The thermoplastic polymer composition comprises: a constitutional unit (i) introduced from 4-methyl-1-pentene; a constitutional unit (ii) introduced from at least one or more kinds of α-olefins selected from α-olefins with a carbon atom number of 2 to 20 other than 4-methyl-1-pentene; a propylene polymer (B); and a propylene polymer (C).

Description

  The present invention relates to a thermoplastic polymer composition containing 4-methyl-1-pentene / α-olefin copolymer and a propylene-based resin, which is excellent in flexibility, tactile sensation, stress relaxation property, shape followability, and the like, and uses thereof. Related.

  Olefin-based synthetic leather (olefin-based leather) is used in various applications such as stationery, various cases, packaging, furniture, construction, and automobile interiors. Examples of soft olefin resins used in such olefin synthetic leather include olefin thermoplastic elastomers, styrene thermoplastic elastomers, ethylene-vinyl acetate copolymers, and ethylene-methacrylic acid copolymers. It has been. However, it has been found that the tactile sensation when touching any of the materials is inferior to that of the main skin, and a polyolefin-based thermoplastic elastomer excellent in texture and tactile sensation is desired.

  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 2 (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.

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.

  As a result of intensive studies to solve such problems, a combination of propylene polymers (B) and (C) having different propylene contents is combined with the 4-methyl-1-pentene / α-olefin copolymer (A). It was found that the stress relaxation property (shape followability) and flexibility are excellent in balance, and that all the above problems can be solved as a skin material.

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), ( 4-methyl-1-pentene / α-olefin copolymer (A), wherein the total of ii) and (iii) is 100 mol%;
(A) / ((B) + (C)) (mass ratio) of the propylene polymer (B) and the propylene polymer (C) is 5/95 to 49/51, preferably 10/90 to 45. / 55 (however, the total of (A) + (B) + (C) is 100 parts by weight).

  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. And the skin material and the molded body made of such a polymer composition have a touch feeling comparable to that of the main skin when touched, and are excellent in texture and touch feeling.

Hereinafter, the present invention will be described in detail, but the present invention is not construed as being limited thereto.
<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) used in the present invention, the structural unit (i) derived from 4-methyl-1-pentene is in the above range. The plastic polymer composition is excellent in flexibility and stress relaxation at room temperature (shape followability).

  The 4-methyl-1-pentene / α-olefin copolymer (A) used in 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 0.5 to 4.0 dl / g, still 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 intrinsic viscosity can be adjusted by adjusting the molecular weight because the molecular weight can be adjusted by using hydrogen together during the polymerization.
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) of the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention, measured by gel permeation chromatography (GPC), is calculated as polystyrene. And preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and still more preferably 1,000 to 2,500,000.

The 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention preferably has a density (measured by 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 . The density can be adjusted by changing the comonomer composition ratio.

  Further, when the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention is made into a sheet, the Shore A hardness (according to JIS K6253) after 15 seconds from the start of the contact with the push needle. It is desirable that the value of the measurement in the state of a press sheet having a thickness of 3 mm is 5 to 90, preferably 10 to 85, and more preferably 15 to 80. The method of creating the press sheet is as shown in the examples.

When the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention is made into a sheet, the Shore A hardness defined by the following formula (according to JIS K6253, thickness It is desirable that the change ΔHS of the value (measured in the state of a 3 mm-thick press sheet) is in the range of 10 to 60, preferably 10 to 50, and 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) used in the present invention, the amount of extraction with methyl acetate is preferably 0 to 1.5% by mass, more preferably 0 to 1. It is desirable that the amount be in the range of 0.0% by mass, more preferably 0 to 0.8% by mass, particularly preferably 0 to 0.7% by 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. Since the methyl acetate extraction amount is derived from an atactic component having low regularity, polymerization may be carried out so that the atactic component is reduced by selecting a catalyst.

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

  The 4-methyl-1-pentene / α-olefin copolymer (A) used in 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 value of 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. It is desirable to be in the range of ˜4.0.

  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.

  The tan δ peak value and the tan δ peak temperature can be controlled by the comonomer composition or the like. Skin materials and molded products using 4-methyl-1-pentene / α-olefin copolymer (A) having a tan δ peak value and a tan δ peak temperature in the above-mentioned range have stress relaxation properties (shape followability, stress absorbability). ).

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. .

<Propylene polymer (B)>
The propylene polymer (B) which is one of the polymer components contained in the propylene polymer composition of the invention has a syndiotactic pentad fraction (rrrr fraction) of 85 measured by ¹³ C-NMR. % Or more, preferably 90% or more, more preferably 93% or more, still more preferably 94% or more, and 90 to 100 mol%, preferably 92 to 100 mol%, more preferably 95 to 100% by structural unit derived from propylene. A propylene-based polymer containing ˜100 mol%.

The propylene polymer (B) having an rrrr fraction in the above range is excellent in moldability, heat resistance and transparency, and has better properties as crystalline polypropylene.
The syndiotactic pentad fraction (rrrr fraction) of the propylene-based polymer (B) used in 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 polymer (B) used in the present invention is a homopolymer of propylene, or propylene and 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, and 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 (B) used in the present invention preferably has 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. It is. The upper limit of the heat of fusion (ΔH _C ) is not particularly limited, but is usually 120 J / g or less.

  The propylene-based polymer (B) used in 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, more preferably 150. C. or higher, particularly preferably 155.degree. C. or higher. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example. The propylene polymer (B) having a melting point (Tm) in the above range is excellent in moldability, heat resistance and mechanical properties.

  The propylene-based polymer (B) used in 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. More preferably, it is desirably in the range of 1.0 to 4 dl / g. When the intrinsic viscosity is in such a range, it exhibits good fluidity and is easily blended with other components. The polymer composition tends to provide a molded article having excellent mechanical strength.

  The propylene polymer (B) used in the present invention is not particularly limited as long as the propylene polymer composition obtained by blending the propylene polymer (B) can be molded, but is usually 230. The MFR measured under a load of 2.16 kg at ° C is 0.001 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min, more preferably 0.1 to 10 g / 10 min.

Propylene Polymer (B) Production Method The propylene polymer (B) used in the present invention can be produced by various known production methods, for example, the production method described in International Publication No. WO2006 / 123759. can get.

<Propylene-based copolymer (C)>
The propylene-based copolymer (C), which is one of the polymer components contained in the thermoplastic polymer composition of the present invention, has a propylene-derived constitutional unit 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 60 to 89 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms, It is a propylene-type copolymer satisfying (c1).

(C1) The intrinsic viscosity [η] (dl / g) measured in decalin at 135 ° C. 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 polymer (B) satisfying the formula (2), preferably the formula (3), of the above (c1) has a large MFR with the same intrinsic viscosity [η] as compared with the conventional isotactic propylene 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, (c1) 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 so-called syndiotactic. It is considered to have a structure. In this case, the resulting propylene polymer composition is excellent in wear resistance.

  The propylene-based copolymer (C) used in the present invention has propylene and 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-eicosene and the like can be mentioned. As the α-olefin copolymerized with propylene, ethylene or the number of carbon atoms is 4-10 alpha olefins are preferred. The α-olefin copolymerized with propylene may be one type or two or more types.

  The propylene-based copolymer (C) used in 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 no melting point. 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 (C) used in the present invention is not particularly limited as long as the propylene polymer composition obtained by mixing the propylene copolymer (C) can be molded. The MFR measured under a load of 2.16 kg at 230 ° C. is 0.01-100 g / 10 min, preferably 0.01-50 g / 10 min, more preferably 0.1-30 g / 10 min, particularly preferably 0. .1-10 g / 10 min.

  The propylene copolymer (C) used in 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 in the range of 0.1 to 5 dl / g. When the propylene polymer (C) having an intrinsic viscosity [η] in the above range is used, the resulting propylene polymer composition has excellent fluidity during molding, and the mechanical properties of the resulting molded article are sufficient. is there.

In the propylene polymer (C) used in the present invention, the Mw / Mn (polystyrene conversion) measured by GPC is usually 1.2 to 3.5, more preferably 1.5 to 3.0. is there.
The propylene copolymer (C) used in 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 component (C) has a higher proportion of so-called syndiotactic structures, and is an index having a meaning similar to satisfying the above-described formula (b4).

  When the propylene polymer (C) used in the present invention satisfies the condition (c1), the constituent unit derived from propylene is, for example, 40 to 89 mol%, preferably 50 to 89 mol%, more preferably 55 to 80 mol. %, For example, 1 to 35 mol%, preferably 1 to 30 mol%, more preferably 5 to 20) mol% of structural units derived from ethylene, and 10 to 10 structural units derived from α-olefins having 4 to 20 carbon atoms. The propylene / ethylene / C4-20 α-olefin copolymer (C1) is preferably contained in an amount of ˜45 mol%, preferably 10 to 40 mol%, more preferably 15 to 40 mol%. 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 polymer (C) used in the present invention satisfies the condition (c1), in addition to the propylene / ethylene / α-olefin copolymer (C1), for example, 50 units of propylene-derived structural units are used. To 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% % Propylene / ethylene copolymer (C2). When (C1) is compared with (C2), a propylene / ethylene / α-olefin copolymer (C1) is preferred.
By using the propylene-based polymer (C) and combining with the polymer (A), a composition having excellent wear resistance can be obtained.

Production Method of Propylene Polymer (C) The propylene polymer (C) used in 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.

<Other resins (D)>
The other resin (D) used in the present invention does not satisfy any of the requirements described in the above (A), (B), (C), for example, thermoplastic resin, elastomer, copolymer rubber Etc. Specific examples include the following resins.

Thermoplastic polyolefin resin (except for the polymer according to the present invention, the same applies hereinafter); for example, low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, poly 1-butene, poly 4 Methyl-1-pentene, poly-3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, cyclic olefin copolymer, Chlorinated polyolefin,
Thermoplastic polyamide resin; for example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
Thermoplastic polyester resin; for example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer,
Thermoplastic vinyl aromatic resin; for example, polystyrene, ABS resin, AS resin, styrene elastomer (styrene / butadiene / styrene block polymer, styrene / ethylene / butene / styrene block polymer, styrene / isobutylene / styrene block polymer, Hydrogenated product),
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene / vinyl acetate copolymer; ethylene / methacrylic acid acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; polyvinyl alcohol; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide polyimide; Polyarylate; Polysulfone; Polyethersulfone; Rosin resin; Terpene resin and petroleum resin;
Copolymer rubber; for example, ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene Examples thereof include rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber.

  Examples of polypropylene include isotactic polypropylene, which may be homopolypropylene, propylene / C2-C20 α-olefin (excluding propylene) random copolymer, or propylene block copolymer. It may be.

  Poly-4-methyl-1-pentene is different from the above copolymer, and is a homopolymer of 4-methyl-1-pentene or a 4-methyl-1-pentene content of 80 to 99.9% by weight. 4-methyl-, preferably 90-99.9% by weight, C2-C20, preferably 6-20 alpha-olefin content 0.1-20% by weight, preferably 0.1-10% by weight 1-pentene / α-olefin random copolymer. In the case of 4-methyl-1-pentene / α-olefin random copolymer, the α-olefin copolymerized with 4-methyl-1-pentene includes ethylene, propylene, 1-butene, 1-hexene and 1-octene. , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., and an α-olefin having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms. These can be used alone or in combination of two or more. The melt flow rate (MFR; ASTM D1238, 260 ° C., 5.0 kg load) of poly-4-methyl-1-pentene should be within the range of 0.1 to 200 g / 10 minutes, preferably 1 to 150 g / 10 minutes. Is desirable. A commercially available product can be used as poly-4-methyl-1-pentene, and examples thereof include TPX (trade name) manufactured by Mitsui Chemicals. Poly 4-methyl-1-pentene from other manufacturers can be preferably used as long as the above requirements are satisfied.

  As the polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and high pressure method low density polyethylene, which are produced by a conventionally known method, can be used.

  The polybutene is a homopolymer of 1-butene or a copolymer of 1-butene and an olefin excluding 1-butene. Examples of the olefin include those described above, and these olefins are used alone or in combination of two or more. Examples of the copolymer include 1-butene / ethylene random copolymer, 1-butene / propylene random copolymer, 1-butene / methylpentene copolymer, 1-butene / methylbutene copolymer, 1-butene / Examples include propylene / ethylene copolymers. In such a copolymer, from the viewpoint of heat resistance, the 1-butene content is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 85% or more. .

  Examples of ethylene / α-olefin copolymers, propylene / α-olefin copolymers, butene / α-olefin copolymers include ethylene / propylene random copolymers, ethylene / 1-butene random copolymers, Ethylene / propylene / 1-butene random copolymer, ethylene / 4-methyl-1-pentene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer, ethylene / propylene / Ethylidene norbornene random copolymer, ethylene / propylene / vinyl norbornene random copolymer, ethylene / 1-butene / ethylidene norbornene random copolymer, ethylene / 1-butene / 1-octene random copolymer, propylene / 1-butene Random copolymer, propylene / ethylene -Butene random copolymer, propylene / 1-hexene random copolymer, propylene / 1-octene random copolymer, butene / 1-hexene random copolymer, butene / 1-octene random copolymer, etc. .

  Among these, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / propylene / 1-butene random copolymer, ethylene / 1-butene / 1-octene random copolymer, ethylene 1-hexene random copolymer, ethylene / 1-octene random copolymer, propylene / 1-butene random copolymer, propylene / ethylene / 1-butene random copolymer, propylene / 1-hexene random copolymer , Propylene / 1-octene random copolymer and the like are particularly preferably used. Commercially available products can also be used, such as Tuffmer (trade name) manufactured by Mitsui Chemicals, ENGAGETM and VERSIFYTM manufactured by Dow Chemical Co., and VistamaxxTM manufactured by ExxonMobil Chemical.

  Examples of rosin resins include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated substances can also be mentioned.

  Examples of the terpene-based resin include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., α-pinene, β-pinene, limonene, dipentene, etc. An aromatic modified terpene resin obtained by polymerizing an aromatic monomer may also be used. Moreover, these hydrogenated substances can also be mentioned.

  Examples of the petroleum resin include an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a co-polymer of C9 fraction), a coumarone indene resin containing styrenes, indenes, coumarone, other dicyclopentadiene, etc. of the tar naphtha fraction, p-tert-butylphenol and Examples thereof include alkylphenol resins typified by condensates of acetylene, xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.

  One or more resins selected from the group consisting of rosin resins, terpene resins, and petroleum resins are preferably hydrogenated derivatives because they are excellent in weather resistance and discoloration resistance. The softening point of the resin by the ring and ball method is preferably in the range of 40 to 180 ° C. The number average molecular weight (Mn) molecular weight measured by GPC of the resin is preferably in the range of about 100 to 10,000. Commercial products may be used as one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins.

Moreover, a commercial item can also be used as these resin.
The other resin (D) of the present invention can be used alone or in combination of two or more of these thermoplastic resins.

  Moreover, the other resin (D) described in the present invention can be used even in a state where two or more of the above resins are partially crosslinked and dynamically crosslinked. Specifically, for example, an olefin thermoplastic elastomer obtained by dynamically crosslinking a mixture containing an α-olefin copolymer rubber and a crystalline polyolefin.

Olefin-based thermoplastic elastomer / crystalline polyolefin Crystalline polyolefin constituting olefin-based thermoplastic elastomer is a crystalline polyolefin obtained by polymerizing one or more α-olefins by either high-pressure method or low-pressure method. It is a polymer. Such crystalline polyolefins include, for example, isotactic and syndiotactic α-olefin polymers, and representative polymers of these are commercially available.

  Specific examples of the α-olefin constituting the crystalline polyolefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 5-methyl-1-hexene, 1-octene and 1-decene can be exemplified. The crystalline polyolefin may be a homopolymer of the α-olefin or a copolymer with two or more α-olefins.

  As the crystalline polyolefin resin, in particular, an isotactic polypropylene having a propylene content of 70 mol% or more, preferably a propylene content of 80 mol% or more is suitably used.

The crystalline polyolefin may be a random copolymer or a block copolymer.
The crystalline polyolefin preferably has an MFR (JIS K 7210, 2.16 kg load, 230 ° C.) usually in the range of 0.01 to 100 g / 10 minutes, particularly 0.05 to 50 g / 10 minutes.

The crystalline polyolefin preferably has a melting point (Tm) determined from an endothermic curve of DSC of 120 to 165 ° C, and more preferably in the range of 130 to 160 ° C.
The crystalline polyolefin is usually used in a proportion of 10 to 60 parts by mass, preferably 20 to 55 parts by mass, in 100 parts by mass of the total amount of the crystalline polyolefin and the α-olefin copolymer rubber.

Α-olefin copolymer rubber The α-olefin polymer rubber (C2-2) constituting the olefin thermoplastic elastomer is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. And a rubber obtained by copolymerizing a non-conjugated polyene such as a non-conjugated diene as necessary.

  Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-decene, 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, Examples thereof include 12-ethyl-1-tetradecene.

  As the α-olefin polymer rubber (C2-2), the above α-olefin may be used singly or as a mixture of two or more. When 4-methyl-1-pentene and other α-olefin are used as a mixture, the molar ratio of 4-methyl-1-pentene to other α-olefin (other α-olefin / 4-methyl- 1-pentene) is preferably in the range of 10/90 to 95/5.

Of the α-olefins, ethylene, propylene, and 1-butene are particularly preferably used.
The α-olefin copolymer rubber (C2-2) is, for example, a copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms, and is derived from ethylene. Examples thereof include ethylene / alpha-olefins having 3 or more carbon atoms (molar ratio) of 40 / 60-95 / 5, which is the ratio between the structural units and the alpha-olefin-derived structural units having 3 or more carbon atoms.

  Specific examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl- , 5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1 , 4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1 , 5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1 , 6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1 , 4-Decadien 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, Examples include 9-methyl-1,8-undecadiene. Among them, in particular, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 4-ethylidene-8-methyl-1, 7-nonadiene (EMND) is preferred.

  The α-olefin polymer rubber may be used singly or as a mixture of two or more kinds when it contains a non-conjugated polyene as described above, for example, a non-conjugated diene. Furthermore, in addition to the non-conjugated polyene as described above, other copolymerizable monomers may be used as long as the object of the present invention is not impaired.

  In the α-olefin polymer rubber, when the non-conjugated polyene is copolymerized, the content of the structural unit derived from the non-conjugated polyene in the copolymer is 0.01 to 30 mol%, preferably It is in the range of 0.1 to 20 mol%, particularly preferably 0.1 to 10 mol% (however, the total amount of the structural units in the α-olefin copolymer rubber is 100 mol%).

  As the α-olefin copolymer rubber, a copolymer of an α-olefin and a non-conjugated polyene is preferable. In particular, an ethylene / C3 or higher α-olefin / non-conjugated polyene copolymer, which is a ratio of ethylene and C3 or higher α-olefin, ethylene / C3 or higher α-olefin (molar ratio). ) Is 40/60 to 95/5, and preferably contains 0.01 to 30 mol% of a structural unit derived from non-conjugated polyene.

  The α-olefin copolymer rubber usually has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. in the range of 1.0 to 10.0 dl / g, preferably 1.5 to 7 dl / g. is there. Moreover, although there is no restriction | limiting in particular, It is preferable that melting | fusing point (Tm) calculated | required from the endothermic curve of DSC of the said alpha-olefin type copolymer rubber (C2-2) does not exist, or exists below 120 degreeC.

The α-olefin copolymer rubber is used in a proportion of 90 to 40 parts by mass, preferably 80 to 45 parts by mass, in a total amount of 100 parts by mass of the crystalline polyolefin and the α-olefin copolymer rubber.
The α-olefin copolymer rubber can be produced by the following method. The α-olefin copolymer rubber is obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms and, if necessary, a non-conjugated diene in the presence of an olefin polymerization catalyst.

-Production method of olefinic thermoplastic elastomer The olefinic thermoplastic elastomer is, for example, a crystalline polyolefin, an α-olefinic copolymer rubber, and a softener and / or an inorganic filler blended as necessary. The mixture is obtained by dynamically heat-treating and partially cross-linking in the presence of an organic peroxide as described below.

  Here, “dynamically heat-treating” means kneading in a molten state. Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate , Tert-butylperoxyisopropyl carbonate, diacetylperoxa Id, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

  Such an organic peroxide is 0.02 to 3 parts by mass, preferably 0.05 to 1 with respect to 100 parts by mass of the total amount of the object to be treated, that is, the crystalline polyolefin and the α-olefin copolymer rubber. It is used in such an amount that it becomes part by mass. If this blending amount is in the above range, the resulting thermoplastic elastomer is adequately crosslinked, and therefore has sufficient heat resistance, moldability, etc., and in some cases, tensile properties, elastic recovery, rebound resilience, etc. Excellent.

  Peroxy crosslinking aids such as sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, N′-m-phenylenedimaleimide, and the like during partial crosslinking treatment with an organic peroxide, Or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, acrylic methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate. You may mix | blend.

  By using a compound such as the above-mentioned crosslinking aid, a uniform and mild crosslinking reaction can be expected. Such a crosslinking assistant or a compound such as a polyfunctional vinyl monomer is usually 2 parts by mass or less, more preferably 0.3 to 1 part by mass with respect to 100 parts by mass of the whole object to be treated. Used in

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese Decomposition accelerators such as naphthenates such as magnesium, lead, and mercury may also be used.

The dynamic heat treatment 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 ranges from the melting point of the crystalline polyolefin to 300 ° C., and is usually 150 to 250 ° C., preferably 170 to 225 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10～100,000Sec ^-1 as the shear rate is preferably 100~50,000sec ^-1.

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

By the dynamic heat treatment described above, an olefinic thermoplastic elastomer composed of crystalline polyolefin and α-olefinic copolymer rubber or partially crosslinked is obtained.
When the olefinic thermoplastic elastomer as described above is used as the other resin (D), the tactile sensation can be improved, and the hardness and stress relaxation properties can be further enhanced.

<Thermoplastic polymer composition>
The thermoplastic polymer composition of the present invention comprises the 4-methyl-1-pentene / α-olefin copolymer (A), the propylene polymer (B) and the propylene polymer (C) (A). / ((B) + (C)) (mass ratio) is in the range of 5/95 to 49/51, preferably 10/90 to 45/55 (however, (A) + (B) + (C) Is a thermoplastic polymer composition).

  The ratio ((B) + (C)) (mass ratio) of the propylene polymer (B) and the propylene polymer constituting the thermoplastic polymer composition is 5/95 to 90/10, preferably It is included in the range of 10/90 to 75/25 (however, the total of ((B) + (C) is 100 parts by weight).

When both the propylene polymer (B) and the propylene polymer (C) are preferably used, a composition excellent in wear resistance, scratch resistance, heat resistance and flexibility can be obtained.
The ratio of the propylene polymer (B) and the propylene polymer (C) is (B) / (C) (mass ratio) of 5/95 to 90/10, preferably 10/90 to 80 /. 20.

By containing (B) and (C) at this ratio, a composition excellent in wear resistance, scratch resistance, heat resistance and flexibility can be obtained.
Or when other resin (D) is included, as for the content, (D) / ((A) + (B) + (C)) (mass ratio) is 0 / 100-90 / 10, Preferably 5 / 95-75 / 25. If it exists in this range, the effect which uses other resin (D) can fully be exhibited.

  The thermoplastic polymer composition of the present invention comprises a 4-methyl-1-pentene / α-olefin copolymer (A), a propylene polymer (B), a propylene polymer (C), and other resins (D ) In the above range can improve flexibility, texture and touch.

  The thermoplastic polymer composition of the present invention comprises the 4-methyl-1-pentene / α-olefin copolymer (A), the propylene polymer (B), the propylene polymer (C), and the like. In addition to resin (D), the composition which contains another component in the range which does not impair the objective of this invention may be sufficient.

  Other components include various weathering stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, slip agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, Examples include dyes, antioxidants, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, crosslinking agents, co-crosslinking agents, crosslinking aids, pressure-sensitive adhesives, softeners, flame retardants, and the like.

  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 such as calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, aluminum hydroxide, aluminum oxide, Examples thereof include magnesium hydroxide, silica, clay, and zeolite, and these can be used alone or in admixture of two or more.

Specific examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petroleum jelly; and coal tar-based coal tar and coal tar pitch. 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.
Typical examples of the flame retardant include magnesium hydroxide, calcium hydroxide, and phosphorus compounds, and these can be used alone or in admixture of two or more.

<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 propylene polymer (B), propylene polymer (C), and other resin (D) are within a predetermined range. It can be obtained by a method of mechanically mixing by various known methods or a method of melt-kneading using an extruder after mixing.

<Molded body obtained from thermoplastic polymer composition and use thereof>
The thermoplastic polymer composition of the present invention can be widely used for conventionally known polyolefin applications. For example, the thermoplastic polymer composition can be molded into various shapes of molded products including sheets, unstretched or stretched films, filaments, and the like. it can. Specifically, as a molded body, molding obtained by a known thermoforming method such as calendar molding, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, foam molding, etc. The body is mentioned.

  Hereinafter, the molded body will be described with several examples. When the molded body according to the present invention is, for example, a calendar molded body, its shape and product type are not particularly limited, and examples thereof include a sheet, a film (unstretched), a pipe, a hose, a wire coating, a filament, and the like. , Films, filaments and the like are preferred.

  When extruding the propylene-based polymer composition of the present invention, conventionally known extruding equipment and molding conditions can be employed. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder Can be formed into a sheet or a film (unstretched) by extruding the molten propylene polymer composition of the present invention from a T-die or the like.

<Sheet molding>
In particular, the propylene-based polymer composition of the present invention is a sheet [generally, a sheet having a large thickness is referred to as a sheet, and a sheet having a thin thickness is referred to as a film. In the present invention, the sheet and the film are collectively referred to as “sheet”. . ] Suitable for molding. When forming a sheet using the propylene-based polymer composition of the present invention,
(Step 1): a step of heating and melting the propylene-based polymer composition;
(Step 2): It can be carried out in a step of forming a sheet of the heat-melted propylene polymer composition.
Further, a step of kneading the heat-melted propylene polymer composition may be included between the (step 1) and the (step 2).

<Calendar molding>
The propylene polymer composition of the present invention is particularly suitable for calendar molding. When calendering using the propylene-based polymer composition of the present invention,
(Step 1): a step of heating and melting the propylene-based polymer composition;
(Step 2-1): It can be performed in a step of forming a sheet by calendering.
Further, a step of kneading the heat-melted propylene polymer composition may be included between the (step 1) and the (step 2-1).
In addition, the (Step 2)
(Step 2-2): A step of obtaining a sheet laminate by a step of simultaneously performing sheet forming and pasting by calendering may be included.

The thermoplastic polymer composition of the present invention can be formed into a molded body by further subjecting a molded body such as a sheet obtained by the above molding method to secondary processing by thermoforming or the like, or laminating 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 performed via an adhesive, but in the case of lamination with polyethylene or polypropylene, lamination using heat adhesion 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 automobile parts that can be used for the molded article of the thermoplastic polymer composition of the present invention include flooring materials, weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, air duct hoses, cup holders, Side brake grip, shift knob cover, seat adjustment knob, flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot, air spats, glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter window gasket , Corner molding, glass encapsulation, hood seal, glass run channel, secondary seal, various packings, bumper parts, body panel, side cover For example, a windshield, a glass run channel, an instrument panel skin, a door skin, a ceiling skin, a seat skin, a weather strip material, a hose, a steering wheel, boots, a wire harness cover, a door trim, a seat adjuster cover, etc. The plastic polymer composition is particularly preferable because it can improve the texture 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 in 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, balls, jumpers, Examples include coats, clothes, bands, bags, ribbons, notebook covers, book covers, key holders, pen cases, wallets, business card holders, periodic holders, and the like. When the thermoplastic polymer composition of the present invention is used, the texture and feel close to natural leather 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 (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 (conforms to JIS K6253)]
A press sheet having a thickness of 3 mm was prepared from the polymer (A) and the composition, used as a measurement sample, and the scale immediately after the start of pressing needle contact and after 15 seconds from the start of pressing needle contact was read.

(Dynamic viscoelasticity)
A press sheet having a thickness of 3 mm was prepared using the polymer (A) and 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%.

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%.

[Propylene polymer (B)]
The propylene resin 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 branch flask having a volume of 30 ml that had been sufficiently purged with nitrogen. 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 polymer (C)]
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 polymer (C) was 62 mol% of propylene-derived structural units, 10 mol% of structural units derived from ethylene, and 28 mol% of structural units derived from 1-butene.

[Other resins (D)]
The following resin was used as other resin (D).
D-1:
Asahi Kasei Corporation Styrene / Ethylene / Butylene / Styrene Copolymer Tuftec H1221
D-2:
Olefin-based thermoplastic elastomer Miralastomer 8030NHS manufactured by Mitsui Chemicals, Inc.
D-3:
After charging 917 mL of dry hexane, 85 g of 1-butene and triisobutylaluminum (1.0 mmol) into a 2000 mL polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 65 ° C. and propylene was used. After pressurizing the system pressure to 0.77 MPa, the system pressure was adjusted to 0.78 MPa with ethylene. Next, a toluene solution obtained by contacting 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride with 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum. Was added to the polymerization vessel, polymerization was carried out for 20 minutes while maintaining the internal temperature at 65 ° C. and the internal pressure at 0.78 MPa with ethylene, and 20 mL of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained copolymer was 60.4 g. The obtained α-olefin copolymer had an ethylene content of 14.0 mol%, a 1-butene content of 19 mol%, MFR = 7 g / 10 min, [η] = 2.0, a melting point = not observed (ΔH : Less than 0.5 J / g), molecular weight distribution (Mw / Mn) = 2.0, mm = 92%, propylene / ethylene / 1-butene copolymer.
D-4:
Propylene / ethylene random copolymer (propylene content: 97.0 mol%, ethylene content: 3.0 mol%, mmmm: 97.5% or more, melting point: 149 ° C, temperature: 230 ° C, load: MFR measured at 2160 g: 20 g / 10 min)

[Example 1]
4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 10 parts by mass, propylene polymer (B): 10.5 parts by mass, propylene polymer (C): 48.5 A thermoplastic polymer composition (Composition 1) was obtained by mixing with parts by weight. 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, the 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 25 parts by mass, and the propylene-based polymer (B): 9.8 parts by mass Parts, propylene polymer (C): 55.2 parts by weight, and when the above (A) + (B) + (C) is 100 parts by weight, other resin (D): Tuftec H1221 manufactured by Asahi Kasei Corporation D-1): A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 2) obtained by mixing 5 parts by weight was used. Various physical properties are shown in Table 2.

Example 3
Instead of the composition 1 used in Example 1, 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 30 parts by mass, and propylene-based polymer (B): 6 parts by mass, Propylene polymer (C): 34 parts by weight, when the above (A) + (B) + (C) is 100 parts by weight, other resin (D): MIRUSTMER 8030NHS (D-2 manufactured by Mitsui Chemicals, Inc.) ): A sample for measurement was prepared in the same manner as in Example 1 except that the thermoplastic polymer composition (Composition 3) obtained by mixing 30 parts by weight was used. Various physical properties are shown in Table 2.

Example 4
Instead of the composition 1 used in Example 1, 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 17 parts by mass, and propylene-based polymer (B): 5 parts by mass, Propylene polymer (C): 28 parts by weight, when the above (A) + (B) + (C) is 100 parts by weight, other resin (D): Tuftec H1221 (D-1) manufactured by Asahi Kasei Corporation : Example 1 with the exception of using a thermoplastic polymer composition (Composition 4) obtained by mixing 17 parts by weight, D-3: 26.4 parts by weight, and D-4: 6.6 parts by weight. A measurement sample was prepared by performing the same operation. Various physical properties are shown in Table 2.

Example 5
Instead of the composition 1 used in Example 1, the 4-methyl-1-pentene / propylene copolymer obtained in Polymerization Example 1: 23 parts by mass, and the propylene-based polymer (B): 4.7 parts by mass. Parts, propylene polymer (C): 26.3 parts by weight, and when the above (A) + (B) + (C) is 100 parts by weight, the other resin (D): Tuftec H1221 manufactured by Asahi Kasei Corporation D-1): 15 parts by weight, D-3: 24.8 parts by weight, D-4: 6.2 parts by weight, except that a thermoplastic polymer composition (composition 5) obtained by mixing was used. Then, the same operation as in Example 1 was performed to prepare a measurement sample. Various physical properties are shown in Table 2.

[Comparative Example 1]
In place of the composition 1 used in Example 1, Miralastomer 8030NHS (D-2) 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 2: 40 parts by weight, and the propylene polymer (B): 9 parts by weight, Propylene polymer (C): A sample for measurement was prepared in the same manner as in Example 1 except that a thermoplastic polymer composition (Composition 7) obtained by mixing 51 parts by weight 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), and
A propylene-based polymer (B) having a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more and containing 90 to 100 mol% of a structural unit derived from propylene; and A propylene-based polymer (C) containing 40 to 89 mol% of a propylene-derived structural unit and 11 to 60 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and
Copolymer (C) has (c1) intrinsic viscosity [η] (dl / g) measured in decalin at 135 ° C. and MFR measured at 230 ° C. under a load of 2160 g. The following relational expression 1.50 × MFR ^{( -0.20)} ≦ [η] ≦ 2.65 × MFR ^(-0.20)
The filling,
Thermoplastic having a mass ratio (A) / ((B) + (C)) of copolymer (A) to copolymer (B) + (C) of 5/95 to 49/51 Polymer composition.   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.   The article according to claim 3, which is an automobile part coated with a skin material.