JP2010018707A - Resin composition and molded product composed of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product having suppressed stickiness in surroundings widely ranging from room temperature to high temperature with almost no loss of flexibility and transparency of a propylene-based elastomer. <P>SOLUTION: The propylene-based resin composition (Y) contains a soft propylene composition (X) comprising a soft polypropylene (A) of 60-100 pts.wt. and a polypropylene (B) of 0-40 pts.wt. (where the sum total of the component (A) and the component (B) is set to be 100 pts.wt.) and a 4-methyl-1-pentene-based polymer (C) of 0.1-15 pts.wt., and is characterized in that the soft polypropylene (A) satisfies relations (A1)-(A3) wherein (A1): its Shore A hardness is in the range of 20-94, (A2): the constitutional unit originating from propylene makes up 51-100 mol% of it, (A3): its melting point observed with DSC is less than 100°C or unobservable, the polypropylene (B) satisfies a relation (B1), (B1): its melting point observed with DSC is 100°C or higher and lower than 175°C, and the 4-methyl-1-pentene-based polymer (C) satisfies a relation (C1), (C1): its intrinsic viscosity (η) measured in a decalin solvent at 135°C is 0.01 dL/g or more and less than 0.50 dL/g. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition comprising a soft propylene composition (X) mainly composed of a soft propylene polymer (A) and a 4-methyl-1-pentene polymer (C), and further to a molded article comprising the same. More specifically, the present invention relates to a molded product in which a sticky feeling is suppressed in a wide range of room temperature to high temperature while maintaining flexibility and transparency at a high level.

  In recent years, propylene-based elastomers containing propylene as a main component are known as soft materials made of polyolefins having excellent flexibility, heat resistance, and transparency, as well as environmental suitability and hygiene (Patent Documents 1 and 2). . Such propylene-based elastomers differ from conventional olefin-based elastomers in that they exhibit excellent transparency, heat resistance (high softening temperature), and scratch resistance, so electrical / electronic equipment parts, industrial materials, furniture, stationery, Although attempts have been made to develop a wide range of uses such as miscellaneous goods, containers / packaging goods, toys, leisure goods, and medical goods, there are cases where the stickiness of the material becomes a problem, and there are cases where the application is limited.

  In order to suppress material stickiness, a conventional method of adding a slip agent (lubricant) is known. For example, Patent Document 3 specifically describes a technique of adding a higher fatty acid amide or higher fatty acid ester to a propylene-based elastomer. Is disclosed.

  However, since such a slip agent (lubricant) is whitened by bleeding on the surface, there is a case where it causes a problem in the product. Further, since the higher fatty acid amides and higher fatty acid esters are eluted in alcohol, there is a problem that they cannot be applied to products in contact therewith.

In order to avoid such a problem, a technique of adding a wax made of a low molecular weight polyolefin is known. Polypropylene wax and polyethylene wax are known as such a wax. However, when such a wax is blended with a propylene elastomer, the effects obtained by the compatibility of both are greatly different. For example, since polyethylene wax is incompatible with propylene elastomer, the transparency of products made of these may be greatly reduced. In addition, since the polypropylene wax has good compatibility with the propylene elastomer, it is considered that the wax component is not effectively localized in the vicinity of the surface and does not exhibit a sufficient sticking suppression effect. Accordingly, there is a demand for a wax having moderate compatibility with the propylene-based elastomer.
Japanese Patent Laid-Open No. 09-309982 WO2004 / 088775 JP 2005-325194 A

  An object of the present invention is to provide a molded article in which the sticky feeling is suppressed in a wide range of room temperature to high temperature without greatly impairing the flexibility and transparency of the propylene-based elastomer.

The present invention comprises the following [I] to [VIII].
[I] 60 to 100 parts by weight of a soft propylene polymer (A), and 0 to 0 of a propylene polymer (B)
40 parts by weight of a soft propylene composition (X) (provided that the total of the components (A) and (B) is 100 parts by weight) and the 4-methyl-1-pentene polymer (C) 0 .1-15
And the soft propylene polymer (A) includes the following (A1) to (A3):
(A1) Shore A hardness is in the range of 20-94.
(A2) The structural unit derived from propylene is 51 to 100 mol%.
(A3) Melting point observed by DSC is less than 100 ° C. or not observed,
The filling,
The propylene polymer (B) is the following (B1)
(B1) The melting point observed by DSC is in the range of 100 ° C. or more and less than 175 ° C.,
The filling,
And the 4-methyl-1-pentene polymer (C) is the following (C1):
(C1) The intrinsic viscosity [η] measured at 135 ° C. in a delican solvent is in the range of 0.01 dl / g or more and less than 0.50 dl / g.
A propylene-based resin composition (Y) characterized by satisfying
[II] The soft propylene polymer (A) is the following (A4) and (A5)
(A4) Propylene and ethylene containing 51 to 90 mol% of propylene-derived structural units, 0 to 49 mol% of ethylene-derived structural units, and 0 to 49 mol% of structural units derived from α-olefins having 4 to 20 carbon atoms Or a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, or a copolymer of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms (where propylene-derived structural units and The total of the structural unit derived from ethylene and the structural unit derived from α-olefin having 4 to 20 carbon atoms is 100 mol%),
(A5) The isotactic triad fraction (mm) calculated by ¹³ C-NMR is 85-99.9%.
And the propylene polymer (B) is (B2)
(B2) The isotactic pentad fraction (mmmm) calculated by ¹³ C-NMR is 90 to 99.8%.
The propylene-based resin composition (Y) according to [I], wherein
[III] The soft propylene polymer (A) is the following (A6) to (A8):
(A6) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 1.2.
(A7) B value specified below is 0.8 to 1.3,

（式中、Ｍ_OEは、プロピレンとエチレンの連鎖と炭素数４以上のα−オレフィンとエチレンの連鎖の合計の、全ダイアッドに対するモル分率を表し、Ｍ_Oはプロピレンと炭素数４
以上のα−オレフィンのモル分率の合計を表し、Ｍ_Eはエチレンのモル分率を表す。）
（Ａ８）ＤＳＣで測定したガラス転移温度（Ｔｇ）が−１０℃〜−５０℃の範囲に観測される、
を満たすことを特徴とする［I］または［II］に記載のプロピレン系樹脂組成物（Ｙ）。
［IV］前記軟質プロピレン組成物（Ｘ）が下記（Ｘ１）および（Ｘ２）
（Ｘ１）ショアーＡ硬度が２０〜９４である、
（Ｘ２）２ｍｍｔプレスシートの内部ヘイズが０．１〜１５％かつ全光線透過率が８０〜９９．９％である、
を満たすことを特徴とする［I］〜［III］のいずれかに記載のプロピレン系樹脂組成物（Ｙ）。
［V］前記４−メチル−１−ペンテン系重合体（Ｃ）が、下記（Ｃ２）〜（Ｃ５）
（Ｃ２）４−メチル−１−ペンテンから導かれる構成単位が、５０〜１００重量％であ
り、４−メチル−１−ペンテン以外の炭素原子数が２〜２０のオレフィンから選ばれる少なくとも１種以上のオレフィンから導かれる構成単位の合計が、０〜５０重量％である４−メチル−１−ペンテン系重合体である、
（Ｃ３）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が１．０〜５．０の範囲にある、
（Ｃ４）示差走査熱量計で測定した融点（Ｔｍ）が１２０〜２４５℃の範囲にある、
（Ｃ５）臨界表面張力が、２２〜２８ｍＮ／ｍの範囲にある、
を満たすことを特徴とする［I］〜［IV］のいずれかに記載のプロピレン系樹脂組成物（
Ｙ）。
［VI］前記４−メチル−１−ペンテン系重合体（Ｃ）が、下記（Ｃ６）
（Ｃ６）下記式（Ｉ）の関係を満たす、
Ａ≦０．２×［η］^(-1.5) ・・・（Ｉ）
（上記式（Ｉ）中、Ａは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した場合の、上記４−メチル−１−ペンテン系重合体中のポリスチレン換算の分子量が１，０００以下となる成分の含有割合（質量％）であり、［η］は上記４−メチル−１−ペンテン系重合体のデリカン溶媒中で１３５℃で測定した極限粘度（ｄｌ／ｇ）である。）
を満たすことを特徴とする［I］〜［V］のいずれかに記載のプロピレン系樹脂組成物（Ｙ）。
［VII］前記４−メチル−１−ペンテン系重合体（Ｃ）が、下記（Ｃ７）
（Ｃ７）¹Ｈ-ＮＭＲにより算出した、上記４−メチル−１−ペンテン系重合体中の末端二重結合量が１０００炭素あたり０．００１個以上０．５個以下である、
を満たすことを特徴とする［I］〜［VＩ］のいずれかに記載のプロピレン系樹脂組成物（Ｙ）。
［VIII］［I］〜［VII］に記載のプロピレン系樹脂組成物（Ｙ）を溶融状態でせん断および／または一軸、二軸、平面伸張の流動を伴って得られる成形体。

(In the formula, M _OE represents the molar fraction of the total of the chain of propylene and ethylene and the chain of α-olefin and ethylene having 4 or more carbon atoms to all dyads, and M 2 _O represents propylene and carbon atoms of 4 carbon atoms.
The total of the mole fractions of the above α-olefins is represented, and M _E represents the mole fraction of ethylene. )
(A8) Glass transition temperature (Tg) measured by DSC is observed in the range of −10 ° C. to −50 ° C.
The propylene-based resin composition (Y) according to [I] or [II], wherein
[IV] The soft propylene composition (X) is the following (X1) and (X2)
(X1) Shore A hardness is 20 to 94,
(X2) The internal haze of the 2 mmt press sheet is 0.1 to 15% and the total light transmittance is 80 to 99.9%.
The propylene-based resin composition (Y) according to any one of [I] to [III], wherein
[V] The 4-methyl-1-pentene polymer (C) is the following (C2) to (C5):
(C2) The structural unit derived from 4-methyl-1-pentene is 50 to 100% by weight, and at least one or more selected from olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene. The total of structural units derived from the olefins is a 4-methyl-1-pentene polymer having 0 to 50% by weight,
(C3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 5.0.
(C4) The melting point (Tm) measured with a differential scanning calorimeter is in the range of 120 to 245 ° C.
(C5) The critical surface tension is in the range of 22-28 mN / m.
The propylene resin composition according to any one of [I] to [IV], wherein
Y).
[VI] The 4-methyl-1-pentene polymer (C) is the following (C6):
(C6) satisfying the relationship of the following formula (I):
A ≦ 0.2 × [η] ^(-1.5) (I)
(In the above formula (I), A is a component having a polystyrene-reduced molecular weight of 1,000 or less in the 4-methyl-1-pentene polymer when measured by gel permeation chromatography (GPC). And [η] is the intrinsic viscosity (dl / g) measured at 135 ° C. in a delican solvent of the 4-methyl-1-pentene polymer.)
The propylene-based resin composition (Y) according to any one of [I] to [V], wherein
[VII] The 4-methyl-1-pentene polymer (C) is the following (C7):
(C7) The amount of terminal double bonds in the 4-methyl-1-pentene polymer calculated by ¹ H-NMR is 0.001 or more and 1000 or less per 1000 carbons,
The propylene-based resin composition (Y) according to any one of [I] to [VI], wherein
[VIII] A molded product obtained by obtaining the propylene-based resin composition (Y) according to [I] to [VII] in a molten state with shearing and / or uniaxial, biaxial, and plane stretching flows.

The propylene-based resin composition (Y) of the present invention can be formed into a molded body in which the feeling of stickiness is suppressed in a wide range of room temperature to high temperature while maintaining flexibility and transparency at a high level.
In addition to the excellent transparency, scratch resistance, whitening resistance, and heat resistance that are characteristic of polypropylene elastomers, these molded products have no stickiness even when used at high temperatures. Can be used under temperature conditions.

Hereinafter, the present invention will be specifically described.
The present invention comprises 60 to 100 parts by weight of a soft propylene polymer (A) and 0 to 40 parts by weight of a propylene polymer (B) having a melting point observed by DSC of 100 ° C. or more and less than 175 ° C. 0.1 to 15 weight of soft propylene composition (X) (however, the total of component (A) and component (B) is 100 parts by weight) and 4-methyl-1-pentene polymer (C) Part.

The soft propylene polymer (A) in the present invention satisfies the following (A1) to (A3).
(A1) Shore A hardness is in the range of 20-94. Preferably it exists in the range of 25-90, More preferably, it is 25-85.
(A2) The structural unit derived from propylene is 51 to 100 mol%. Preferably it is 51-90 mol%, More preferably, it is 60-80 mol%.
(A3) Melting point observed by DSC is less than 100 ° C. or not observed. Preferably less than 90 ° C or not observed, more preferably less than 80 ° C or not observed.

With these physical properties, a soft propylene composition (X) excellent in flexibility, heat resistance, transparency, and low-temperature characteristics (low glass transition temperature) can be obtained.
The molecular structure (stereostructure) of the soft propylene polymer (A) is not particularly limited as long as it is in the above physical property range, and specifically, any of an isotactic structure, a syndiotactic structure, and an atactic structure is used. However, those having an isotactic structure are particularly preferable in terms of good moldability (high solidification speed), excellent mechanical strength and heat resistance.

  In general, in order to obtain a soft propylene polymer (A) satisfying the above requirements (A1) to (A3), (1) the molecular structure regularity of the soft propylene polymer (A) ( There are methods such as (2) copolymerizing a comonomer other than propylene, but when the soft propylene polymer (A) shows an isotactic structure, the method (2) is selected. There is a need.

The soft propylene polymer (A) of the present invention is preferably a copolymer of propylene and ethylene, a copolymer of propylene and α-olefin, or a copolymer of propylene, ethylene and α-olefin. It is preferable to satisfy the following requirements (A4) and (A5).
(A4) Propylene / ethylene containing 51 to 90 mol% of propylene-derived structural units, 0 to 49 mol% of ethylene-derived structural units, and 0 to 49 mol% of structural units derived from α-olefins having 4 to 20 carbon atoms. A copolymer or a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, or a copolymer of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms (where propylene, ethylene and 4 to 20 carbon atoms; The total of 20 α-olefins is 100 mol%).
Preferably, the structural unit derived from propylene is preferably 51 to 90 mol%, more preferably 60 to 89 mol%, still more preferably 62 to 88 mol%, and the structural unit derived from ethylene is preferably 7 to 24 mol%, and more. Preferably 8 to 20 mol%, more preferably 8 to 18 mol%, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is preferably 3 to 25 mol%, more preferably 3 to 20 mol%, still more preferably. Is a copolymer of propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms comprising 4 to 20 mol% (wherein the propylene-derived structural unit, the ethylene-derived structural unit, and the carbon number of 4 to 20 The total of the structural units derived from α-olefin is 100 mol%).
(A5) The isotactic triad fraction (mm) calculated by ¹³ C-NMR is 85-99.9%. Preferably it is 87 to 99.8%.

In addition, the soft propylene polymer (A) of the present invention preferably satisfies the following (A6) to (A8).
(A6) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 1.2. Preferably it is 3.0-1.4, More preferably, it is 2.6-1.6.

The soft propylene polymer (A) having a molecular weight distribution within the above range is preferable because it has a low molecular weight and suppresses stickiness.
(A7) B value prescribed | regulated below is 0.8-1.3. Preferably it is 0.9-1.2, More preferably, it is 0.9-1.1

（式中、Ｍ_OEは、プロピレンとエチレンの連鎖と炭素数４以上のα−オレフィンとエチレンの連鎖の合計の、全ダイアッドに対するモル分率を表し、Ｍ_Oはプロピレンと炭素数４
以上のα−オレフィンのモル分率の合計を表し、Ｍ_Eはエチレンのモル分率を表す。）
Ｂ値が上記範囲にある軟質プロピレン重合体（Ａ）は、後述のプロピレン重合体（Ｂ）との相容性に優れるなどの点において好ましい。Ｂ値が上記範囲より大きい場合、各モノマー（プロピレン、エチレン、炭素原子数４〜２０のα-オレフィン）が交互に結合した
交互共重合体に近い分子一次構造を有することを意味し、このような軟質プロピレン重合体（Ａ）はプロピレン重合体（Ｂ）との相容性が劣ることになる。またＢ値が上記範囲より小さい場合、各モノマーが密集したブロック共重合体に近い分子一次構造を有することを意味し、この場合も軟質プロピレン重合体（Ａ）とプロピレン重合体（Ｂ）との相容性が劣ることになる。
（Ａ８）ＤＳＣで測定したガラス転移温度（Ｔｇ）が−１０℃〜−５０℃の範囲に観測される。好ましくは−１５℃〜−４０℃の範囲に観測される。

(In the formula, M _OE represents the molar fraction of the total of the chain of propylene and ethylene and the chain of α-olefin and ethylene having 4 or more carbon atoms to all dyads, and M 2 _O represents propylene and carbon atoms of 4 carbon atoms.
The total of the mole fractions of the above α-olefins is represented, and M _E represents the mole fraction of ethylene. )
The soft propylene polymer (A) having a B value in the above range is preferable in that it has excellent compatibility with the propylene polymer (B) described later. When the B value is larger than the above range, it means that each monomer (propylene, ethylene, α-olefin having 4 to 20 carbon atoms) has a molecular primary structure close to an alternating copolymer in which the monomers are alternately bonded. Such a soft propylene polymer (A) has poor compatibility with the propylene polymer (B). Further, when the B value is smaller than the above range, it means that each monomer has a molecular primary structure close to a dense block copolymer. In this case as well, the soft propylene polymer (A) and the propylene polymer (B) Compatibility will be inferior.
(A8) A glass transition temperature (Tg) measured by DSC is observed in the range of −10 ° C. to −50 ° C. Preferably, it is observed in the range of −15 ° C. to −40 ° C.

A soft propylene polymer (A) having a glass transition temperature (Tg) in the above range means that it has high stereoregularity (low inversion) and a uniform molecular structure with a narrow composition distribution. Moreover, since the low temperature characteristic of the soft propylene composition (X) of this invention improves, it is very preferable.
In addition, it is preferable that the soft propylene polymer (A) of the present invention further satisfies the following (A9).
(A9) Melt flow rate (MFR) (ASTM D1238, 230 ° C., under 2.16 kg load) is preferably 0.01 to 200 g / 10 minutes, more preferably 0.05 to 100 g / 10 minutes. 0.1 to 50 g / 10 min is more preferable.

When the MFR is in this range, the strength and impact resistance of the soft propylene composition (X) of the present invention, or the moldability when processing these, is preferable.
The production method of the soft propylene polymer (A) of the present invention is not particularly limited, and a known catalyst capable of stereoregular polymerization of an olefin with an isotactic or syndiotactic structure, for example, a solid titanium component and an organic metal It can be produced by polymerizing propylene or copolymerizing propylene and ethylene and / or other α-olefins in the presence of a compound-based catalyst or a metallocene catalyst using a metallocene compound as a component of the catalyst. However, the soft propylene polymer (A) satisfying the requirements of (A4) to (A8) shown as a particularly preferred form is a mixture of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a metallocene catalyst. It is obtained by polymerizing. As the metallocene catalyst, for example, a catalyst described in International Publication No. 2004-087775, for example, a catalyst described in Examples e1 to e5, or the like can be used.

Since the soft propylene polymer (A) satisfying the above range has a specific comonomer composition and high stereoregularity, it exhibits good low-temperature characteristics (low glass transition temperature) and breaking strength. Moreover, since compatibility with a propylene polymer (B) improves, transparency of the soft propylene composition (X) using this also improves.
Propylene polymer (B):
Examples of the propylene polymer (B) in the present invention include a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms including ethylene other than propylene. . Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.

  Specific examples of the propylene polymer (B) include the following polymers. Homopolypropylene with excellent heat resistance (usually known copolymer having less than 3 mol% of α-olefin copolymer component having 2 to 20 carbon atoms including ethylene other than propylene), excellent balance between heat resistance and flexibility Block polypropylene (usually a known one having a normal decane eluting rubber component of 3 to 35 wt%), and also a flexible and transparent random polypropylene (usually α- having 2 to 20 carbon atoms including ethylene other than propylene) The olefin copolymerization component can be selected according to the purpose, such as a known component having an olefin copolymerization component of 3 mol% or more and less than 20 mol%, preferably 3 mol% or more and less than 10 mol%. Moreover, a some propylene polymer (B) can be used together as needed, for example, 2 or more types of components (for example, random polypropylene, homopolypropylene, etc.) from which melting | fusing point and rigidity differ can also be used.

The propylene polymer (B) in the present invention satisfies the following (B1).
(B1) The propylene polymer (B) in the present invention has a melting point observed by DSC of 100 ° C. or higher and lower than 175 ° C. Preferably it exists in the range of 115 to 170 degreeC, More preferably in the range of 130 to 170 degreeC.

The propylene polymer (B) of the present invention preferably satisfies the following (B2).
(B2) For the propylene polymer (B) of the present invention, either an isotactic structure or a syndiotactic structure can be used, but an isotactic structure is particularly preferred, and ¹³ C-NMR The isotactic pentad fraction (mmmm) calculated by the formula (1) is 90 to 99.8%. It is preferably 93% to 99.7%, more preferably 95% to 99.6%.

  When such a propylene polymer (B) is used, the propylene / ethylene that satisfies the requirements of (A1) to (A5) or (A1) to (A8) shown as a preferred form in the above-mentioned soft propylene polymer (A) The copolymer, propylene / α-olefin copolymer or propylene / ethylene / α-olefin copolymer is preferably compatible with each other, and the physical properties of the soft propylene composition (X) are improved.

The propylene polymer (B) of the present invention preferably satisfies the following (B3).
(B3) The melt flow rate (MFR) of the propylene polymer (B) of the present invention (ASTM D1238, 230 ° C., 2.16 kg load) is not particularly limited, but preferably 0.01 to 1000 g / 10 min. More preferably, it is 0.05-400 g / 10min, More preferably, it is 0.1-100 g / 10min.

  The method for producing the propylene polymer (B) of the present invention is not particularly limited and can be obtained by a known method. For example, the solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, an organoaluminum compound, and Propylene is polymerized or copolymerized using propylene and another α-olefin in a Ziegler catalyst system comprising an electron donor or a metallocene catalyst system using a metallocene compound as a component of the catalyst.

Soft propylene composition (X):
The soft propylene composition (X) used in the present invention comprises the soft propylene polymer (A) alone or a mixture of the soft propylene polymer (A) and the propylene polymer (B).

  Here, when the soft propylene composition (X) contains the propylene polymer (B), the soft propylene composition (X) has an effect of improving physical properties such as mechanical properties and heat resistance of the soft propylene composition (X), and heat resistance is required. When the soft propylene composition (X) of the present invention is applied to a use, it is preferable to contain the propylene polymer (B) because it becomes very effective.

  In the soft propylene composition (X), the soft propylene polymer (A) is 60 to 100 parts by weight, preferably 70 to 97 parts by weight, more preferably 75 to 95 parts by weight, and the propylene polymer (B) is 0 to 40 parts by weight. Parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight (provided that the total of component (A) and component (B) is 100 parts by weight).

  The method for obtaining the soft propylene composition (X) used in the present invention is not particularly limited, but the method for obtaining the composition by polymerizing the soft propylene polymer (A) and the propylene polymer (B) simultaneously or sequentially, A method of obtaining the soft propylene polymer (A) and the propylene polymer (B) obtained independently, and further producing one of the soft propylene polymer (A) and the propylene polymer (B) first, For example, there is a method of adding the one manufactured in the process of producing the other one.

  The soft propylene composition (X) of the present invention may contain other polymers as optional components within a range not impairing the object of the present invention. In that case, there is no restriction | limiting in particular in a compounding quantity, For example, it is preferable that it is about 0.1-30 weight part with respect to 100 weight part of soft propylene compositions (X) of this invention.

  Preferred as such another polymer is an ethylene polymer or copolymer containing ethylene as a main component (51 mol% or more), and when these are blended, the flexibility and low temperature of the soft propylene composition (X) Improved characteristics.

  Moreover, it is also one aspect that the polymer component is composed only of a soft propylene polymer (A) and a propylene polymer (B) without containing other elastomers and other resins. In this case, the transparency is particularly excellent.

  The soft propylene composition (X) of the present invention includes a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, and nucleating agent as long as the object of the present invention is not impaired. Additives such as lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants and copper damage inhibitors may be blended as necessary.

  Moreover, the soft propylene composition (X) of the present invention may be graft-modified with a polar monomer or the like. Specifically, it means a form in which at least one or both of the soft propylene polymer (A) and the propylene polymer (B) constituting the soft propylene composition (X) are graft-modified with a polar monomer.

As the soft propylene composition (X) of the present invention, those having the following physical properties (X1) and (X2) are suitable.
(X1) Shore A hardness is 20-94. Preferably it is 25-90, More preferably, it is 25-85.
(X2) The internal haze of the 2 mmt press sheet is 0.1 to 15% and the total light transmittance is 80 to 99.9%. Preferably, the internal haze is 0.1 to 10% and the total light transmittance is 85 to 99.
. 9%.

When the physical properties of the soft propylene composition (X) of the present invention satisfy (X1) and (X2), it is preferable because the resulting molded article has excellent flexibility and transparency.
As the soft propylene composition (X) used in the present invention, those having the following physical properties (X3) are more preferable.
(X3) Melt flow rate (MFR) (ASTM D1238, 230 ° C., 2.16 kg under load) is not particularly limited, but is 0.01 to 1000 g / 10 minutes, preferably 0.05 to 400 g / 10 minutes. More preferably, it is 0.1-100 g / 10min.
4-methyl-1-pentene polymer (C):
The 4-methyl-1-pentene polymer used in the present invention satisfies the following (C1). (C1) The intrinsic viscosity [η] measured at 135 ° C. in a delican solvent is in the range of 0.01 dl / g or more and less than 0.50 dl / g. Preferably it is 0.02-0.45 dl / g, More preferably, it is the range of 0.03-0.40 dl / g. When the intrinsic viscosity [η] is within this range, the resin modifier is excellent in the mold release effect and is excellent in dispersibility in the resin, so that the influence on the mechanical properties is small.

The 4-methyl-1-pentene polymer used in the present invention preferably satisfies the following (C2) to (C5).
(C2) The structural unit derived from 4-methyl-1-pentene is 50 to 100% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, and other than 4-methyl-1-pentene. The total of structural units derived from at least one olefin selected from olefins having 2 to 20 carbon atoms is 0 to 50% by weight, preferably 0 to 40% by weight, more preferably 0 to 30% by weight. 4-methyl-1-pentene polymer.

Examples of the olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene used in the 4-methyl-1-pentene polymer in the present invention include linear or branched α-olefins and cyclics. Examples include olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, and functionalized vinyl compounds.

Specific examples of the linear or branched α-olefin used in the 4-methyl-1-pentene polymer in the present invention include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc., a linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms; For example, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1 -Hexene, 4-ethyl-1-hexene, 3-
Preferably, a branched α-olefin such as ethyl-1-hexene is preferably 5-20, more preferably 5-10.

  Examples of the cyclic olefin include those having 3 to 20 carbon atoms, preferably 5 to 15 such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane and the like.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o
-Mono or polyalkyl styrenes such as ethyl styrene, m-ethyl styrene, p-ethyl styrene.

Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, and 1,3-
Pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3
Examples thereof include those having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as -pentadiene, 1,3-hexadiene, and 1,3-octadiene.

Non-conjugated polyenes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5
-Hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene,
1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 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-
Examples thereof include isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms.

Functionalized vinyl compounds include hydroxyl group-containing olefins, halogenated olefins, acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid and 8-nonenoic acid. , Unsaturated carboxylic acids such as 9-decenoic acid, unsaturated amines such as allylamine, 5-hexeneamine and 6-hepteneamine, (2,7-octadienyl)
Examples of compounds in succinic anhydride, pentapropenyl succinic anhydride and the above unsaturated carboxylic acids, unsaturated acid anhydrides such as compounds in which a carboxylic acid group is replaced with a carboxylic anhydride group, Examples of compounds in acids include unsaturated carboxylic acid halides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid halide group, 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1 Unsaturated epoxy compounds such as -hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene, etc. Is mentioned.

The hydroxyl group-containing olefin is not particularly limited as long as it is a hydroxyl group-containing olefin compound, and examples thereof include terminal hydroxylated olefin compounds. Specific examples of the terminal hydroxylated olefin compound include vinyl alcohol, allyl alcohol, hydroxylated 1-butene, hydroxylated 1-pentene, hydroxylated 1-hexene, hydroxylated 1-octene, and hydroxylated-1 -Decene, hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene, hydroxyl-1-octadecene, hydroxyl-1-eicocene, etc., preferably 2-20, preferably 2 10 linear hydroxylated α-olefins; for example, hydroxylated 3-methyl-1-butene, hydroxylated 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated-3 -Ethyl-1-pentene, hydroxylated-4,4-dimethyl-1-pentene, hydroxylated-4-
Methyl-1-hexene, hydroxylated 4,4-dimethyl-1-hexene, hydroxylated 4-ethyl-1-hexene, hydroxylated 3-ethyl-1-hexene and the like are preferably 5 to 20, more preferably 5 to 10 branched hydroxylated α-olefins.

Specific examples of the halogenated olefin include halogenated α-olefins having a group 17 atom of the periodic table such as chlorine, bromine and iodine, such as vinyl halide, halogenated-1-butene, halogenated-1-pentene, and halogen. -1-hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated A linear halogenated α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as -1-eicosene; for example, halogenated-3-methyl-1-butene, halogenated-4-methyl-1- Pentene, halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl -1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1-hexene, halogenated-3-ethyl-1-hexene Preferably, a branched halogenated α-olefin having 5 to 20 and more preferably 5 to 10 is used.

The olefins used together with 4-methyl-1-pentene may be one kind or a combination of two or more kinds. As the olefins used together with 4-methyl-1-pentene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane, styrene and the like are preferably used.
(C3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.0 to 5.0. Preferably it is 1.0-4.5, More preferably, it is 1.0-4.0, Most preferably, it is 1.0-3.5. When Mw / Mn is within the above range, the content of the low molecular weight region component of the molecular weight distribution can be reduced, and when used as a resin modifier, the stickiness of the molded product can be suppressed and the content of the high molecular weight component can be suppressed. Since the amount can be reduced, the dispersibility in the molded product is excellent, and the influence on the mechanical properties is reduced. Such molecular weight distribution can be produced by thermal decomposition, but is preferably obtained by producing a 4-methyl-1-pentene polymer using a Ziegler catalyst, more preferably a metallocene catalyst described later.
(C4) Melting | fusing point (Tm) measured with a differential scanning calorimeter is 120-245 degreeC, Preferably it is 130-240 degreeC, More preferably, it is 140-235 degreeC. When the melting point (Tm) is in this range, the balance between molding processability when used as a resin modifier and blocking resistance when storing a 4-methyl-1-pentene polymer is excellent. The melting point of the 4-methyl-1-pentene polymer depends on the number average molecular weight (Mn) when it is a homopolymer of 4-methyl-1-pentene. For example, if the molecular weight of 4-methyl-1-pentene homopolymer is lowered, the melting point of the resulting polymer can be controlled low. When the 4-methyl-1-pentene polymer is a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene, The melting point of the -1-pentene polymer depends on the number average molecular weight (Mn), and the number of carbon atoms other than 4-methyl-1-pentene relative to 4-methyl-1-pentene during polymerization is 2 to 2. It can be controlled by the amount and type of 20 olefins used. For example, when the amount of olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene relative to 4-methyl-1-pentene is increased, the melting point of the resulting polymer can be lowered.
(C5) The critical surface tension is 22 to 28 mN / m, preferably 23 to 27.5 mN / m, and more preferably 24 to 27.5 mN / m. When the critical surface tension is within this range, excellent release properties can be imparted to the molded product. Such critical surface tension depends on the 4-methyl-1-pentene constituent unit in the 4-methyl-1-pentene polymer, and in order to obtain the preferred critical surface tension, 4-methyl-1 The amount of 4-methyl-1-pentene in the pentene polymer (C) is 20 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight.

The 4-methyl-1-pentene polymer used in the present invention more preferably satisfies the following (C6).
(C6) The relationship of the following formula (I) is satisfied.
A ≦ 0.2 × [η] ^(-1.5) (I)
(In the above formula (I), A is a component having a polystyrene-reduced molecular weight of 1,000 or less in the 4-methyl-1-pentene polymer when measured by gel permeation chromatography (GPC). And [η] is the intrinsic viscosity (dl / g) measured at 135 ° C. in a delican solvent of the 4-methyl-1-pentene polymer.) (I) When a 4-methyl-1-pentene polymer satisfying the formula is used, the releasability of the molded product can be improved, and the mechanical properties of the molded product are not impaired. The 4-methyl-1-pentene polymer satisfying the condition of the above formula (I) can be preferably produced using a metallocene catalyst described later.

  Usually, when a 4-methyl-1-pentene polymer having a low intrinsic viscosity is blended with a propylene polymer as a resin modifier and molding is performed, a 4-methyl-1-pentene polymer having a lower molecular weight is used. The coalescence is predicted to be localized in the vicinity of the inner wall surface in order to reduce shear acting on the inner wall surface of the molding machine such as a screw, barrel, die, etc. in the molten state. Even in the process of solidifying the molded body from the die or the like, the localized state is maintained, and as a result, the 4-methyl-1-pentene polymer tends to be present on the surface layer of the molded article, and the molded product is separated. It is thought that the type will increase. However, even if the releasability is increased, the 4-methyl-1-pentene polymer itself may be blocked or the mechanical properties of the molded product may be impaired. Moreover, the mold release effect of the obtained molded product may not be sufficient.

  As a result of studies by the present inventors, it has been found that the proportion of components having a molecular weight of 1,000 or less in the 4-methyl-1-pentene polymer is extremely important in relation to the intrinsic viscosity. Although the detailed mechanism is not clear, it is considered that a component having a molecular weight of 1,000 or less is particularly sticky among 4-methyl-1-pentene polymers. Therefore, it is presumed that the release effect cannot be sufficiently obtained as a resin modifier unless the component having a molecular weight of 1,000 or less is made a certain ratio or less. It is also considered that the 4-methyl-1-pentene polymer itself is easily blocked. Furthermore, it is presumed that a component having a particularly low molecular weight such as a molecular weight of 1,000 or less also causes a decrease in mechanical properties.

As the 4-methyl-1-pentene polymer used in the present invention, one satisfying the following (C7) is particularly suitable.
(C7) The amount of terminal double bonds in the 4-methyl-1-pentene polymer calculated by ¹ H-NMR is 0.001 or more and 100 or less per 1000 carbons, preferably 1000 It is preferably 0.001 or more and 0.5 or less per carbon, more preferably 0.001 or more and 0.4 or less, and particularly preferably 0.001 or more and 0.3 or less. Such terminal double bond amount can be produced by thermal decomposition, but is preferably obtained by producing a 4-methyl-1-pentene polymer using a Ziegler catalyst, more preferably a metallocene catalyst described later. It is done.
(C8) The 4-methyl-1-pentene polymer used in the present invention preferably has an iodine value of 0.001 g / 100 g or more and 180 g / 100 g or less, more preferably 0.001 g / 100 g or more and 0.9 g / 100 g or less. More preferably, it is 0.001 g / 100 g or more and 0.7 g / 100 g or less, and most preferably 0.001 g / 100 g or more and 0.5 g / 100 g or less. Such iodine value can be produced by thermal decomposition, but is preferably obtained by producing a 4-methyl-1-pentene polymer using a Ziegler catalyst, more preferably a metallocene catalyst described later.

The iodine value of the 4-methyl-1-pentene polymer was measured by the following method. That is, 2 g of 4-methyl-1-pentene polymer is dissolved in 100 ml of decalin at 150 ° C., allowed to stand at room temperature until 50 ° C., and then 20 ml of acetic acid in which 1 mmol of iodine monochloride is dissolved is added. After standing in a dark place for 30 minutes with occasional stirring, 20 ml of 10% aqueous potassium iodide solution was added and titrated with 0.1N aqueous sodium thiosulfate solution. The iodine value indicating the number of g of iodine added to a 100 g sample was calculated by the following formula.

Iodine number = 1.269 (B-A) / C
Here, A and B are the number of ml of sodium thiosulfate required for titration in the sample and the blank experiment, respectively, and C is the number of grams of the sample.
(C9) The 4-methyl-1-pentene polymer used in the present invention has an n-decane soluble content at 10 ° C. of 0.01 wt% or more and 99 wt% or less (the 4-methyl-1-pentene described above). (Based on 100% by weight of the polymer). More preferably, they are 0.01 weight% or more and 80 weight% or less, More preferably, they are 0.01 weight% or more and 40 weight% or less. In order to obtain such an n-decane soluble amount, thermal decomposition and production with a Ziegler catalyst are possible, but production with a metallocene catalyst described later is preferred. The amount of n-decane solubles added was about 3 g of 4-methyl-1-pentene polymer added to 450 ml of n-decane, dissolved at 145 ° C., cooled to 10 ° C., and filtered to remove the n-decane insoluble part. The n-decane soluble part was collected from the filtrate.
(C10) The 4-methyl-1-pentene polymer used in the present invention preferably has an isodyad tacticity calculated by ¹³ C-NMR of 70% to 99%, more preferably 80 to 99%, still more preferably. Is 90 to 99%, particularly preferably 93 to 99%. Such isodyad tacticity can be produced by thermal decomposition, but is preferably obtained by producing a 4-methyl-1-pentene polymer using a Ziegler catalyst, more preferably a metallocene catalyst described later. . Isodyad tacticity was measured by the following method.

The isodyad tacticity of a 4-methyl-1-pentene polymer is expressed as the isobutyl when an arbitrary two head-to-tail 4-methyl-1-pentene unit chain in a polymer chain is expressed in a planar zigzag structure. It was defined as the ratio in which the direction of branching was the same and was determined from the ¹³ C-NMR spectrum by the following formula.

Isodiad tacticity (%) = [m / (m + r)] × 100
In the formula, m and r are the following formulas

で表される頭-尾で結合している４-メチル-１-ペンテン単位の主鎖メチレンに由来する吸収強度を示す。

The absorption intensity derived from the main chain methylene of 4-methyl-1-pentene units bonded at the head-tail represented by

^{For the 13} C-NMR spectrum, a nuclear magnetic resonance apparatus having a ¹ H resonance frequency of 400 MHz was used, and a sample was measured in an NMR sample tube (5 mmφ) with about 0.5 ml of hexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene. The solution was completely dissolved in a solvent to which about 0.05 ml of deuterated benzene as a lock solvent was added, and then measured at 120 ° C. by a proton complete decoupling method. As measurement conditions, a flip angle of 45 ° and a pulse interval of 5 sec or more are selected. The chemical shift was set at 127.7 ppm of benzene, and the chemical shifts of other carbon peaks were based on this.

For the peak region, the region of 41.5 to 43.3 ppm was divided by the minimum points of the peak profile, and the high magnetic field side was classified as the first region and the low magnetic field side was classified as the second region. In the first region, the main chain methylene in the 2-chain 4-methyl-1-pentene unit represented by (m) resonates, but the methylene peak connected to the comonomer also overlaps. The integrated value obtained by subtracting the doubled peak area derived from ˜35.5 ppm comonomer was defined as “m”.

In the second region, the 4-methyl-1-pentene unit 2-chain main chain methylene represented by (r) resonated, and the integrated value was defined as “r”.
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 10,000 times or more.

A method for producing the 4-methyl-1-pentene polymer used in the present invention will be described.
The 4-methyl-1-pentene polymer used in the present invention may be obtained by directly polymerizing olefins, or thermally decomposes a high molecular weight 4-methyl-1-pentene polymer. In addition, a solvent fractionation method in which these 4-methyl-1-pentene polymers are fractionated by a difference in solubility in a solvent, or a molecular distillation method in which fractionation is performed by a difference in boiling points is used. And may be purified.

For the production of the 4-methyl-1-pentene polymer used in the present invention, a conventionally known catalyst, for example, a magnesium-supported titanium catalyst, WO 01/53369, WO 01/27124, A metallocene catalyst described in JP-A-3-193396 or JP-A-02-41303 is preferably used. More preferably, an olefin polymerization catalyst using a metallocene compound represented by the following general formula (1) or (2) is suitably used for the production of the 4-methyl-1-pentene polymer used in the present invention. It is done.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は水素、炭化水素基、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、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または異なる組合せで選んでもよく、ｊは１〜４の整数である。）
上記一般式（１）または（２）のＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は水素、炭化水素基、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い。

(In the formula, 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 , R ¹⁴ are hydrogen and hydrocarbon. group, selected from a silicon-containing hydrocarbon group, which may be the same as or different from each other, adjacent substituents of R ¹ to R ⁴ may be bonded to each other to form a ring, R ⁵
To R ¹² may be bonded to each other to form a ring, and A is a divalent group having 2 to 20 carbon atoms that may partially contain an unsaturated bond and / or an aromatic ring. A may contain two or more ring structures including a ring formed with Y, M is a metal selected from Group 4 of the periodic table, and Y is carbon or silicon. Q may be selected from the same or different combinations from halogens, hydrocarbon groups, anionic ligands, or neutral ligands capable of coordinating with a lone pair, and j is an integer of 1 to 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. And may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 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, naphthyl, tolyl, etc. Can be mentioned.

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. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl. Etc. R ¹ and R ³ are hydrogen, and R ² is preferably a hydrocarbon group or a silicon-containing hydrocarbon group, and R ² is more preferably a sterically bulky substituent, R ² Is particularly preferably a substituent having 4 or more carbon atoms.

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 substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is 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 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, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl Examples thereof include tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene, and the 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. Preferable specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroin Examples include danylidene, 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, 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. 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, 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 WO01 / 27124, but the scope of the present invention is not particularly limited thereby.

When the production of the 4-methyl-1-pentene polymer in the present invention is performed using a metallocene catalyst, the catalyst component is (i) a metallocene compound represented by the above general formula (1) or (2),
(Ii) (ii-1) organometallic compounds,
(ii-2) an organoaluminum oxy compound, and
(ii-3) at least one compound selected from compounds that react with the metallocene compound (i) to form an ion pair,
If necessary,
(Iii) It can be used as a polymerization catalyst by a generally known method composed of a particulate carrier, and for example, the method described in WO01 / 27124 can be employed.

In 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. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. Olefins containing 4-methyl-1-pentene used in the process can be used as a solvent.

In carrying out the polymerization, component (i) is generally used in an amount of 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol, per liter of reaction volume.
Component (ii-1) has a molar ratio [(ii-1) / M] of component (ii-1) to transition metal atom (M) in component (i) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (ii-2) has a molar ratio [(ii-2) / M] of the aluminum atom in component (ii-2) and the transition metal atom (M) in component (i) usually 10 to 10. 5000, preferably 20-
The amount used is 2000. Component (ii-3) has a molar ratio [(ii-3) / M] of component (ii-3) to transition metal atom (M) in component (i) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually −50 to
It is 400 degreeC, Preferably it is 10-300 degreeC, More preferably, it is the range of 10-250 degreeC. If the polymerization temperature is too low, the polymerization activity per unit catalyst is lowered, which is not industrially preferable.

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

  In the polymerization, hydrogen can be added for the purpose of controlling the molecular weight, intrinsic viscosity [η] and polymerization activity of the produced polymer, and the amount is suitably about 0.001 to 100 NL per kg of olefin.

The 4-methyl-1-pentene polymer in the present invention is, for example, charged amount of 4-methyl-1-pentene and olefin having 2 to 20 carbon atoms, kind of polymerization catalyst, polymerization temperature, hydrogenation at the time of polymerization. By adjusting the amount and the like, it can be made differently by controlling the melting point, stereoregularity and molecular weight, intrinsic viscosity [η] and the like.

The 4-methyl-1-pentene polymer in the present invention may be used in the form of powder or pellets.
Propylene-based resin composition (Y), molded article comprising the same:
The propylene resin composition (Y) of the present invention is preferably 0.1 to 15 parts by weight of 4-methyl-1-pentene polymer (C), preferably 100 parts by weight of the soft propylene composition (X). Contains 0.5 to 12 parts by weight, more preferably 1 to 10 parts by weight.

  The mixed form of the soft propylene composition (X) and the 4-methyl-1-pentene polymer (C) is not particularly limited, but as a preferred form, the soft propylene composition (X) obtained by the above method and A form in which 4-methyl-1-pentene polymer (C) is mixed in a solid state (usually referred to as dry blend), or soft propylene composition (X) and 4-methyl-1-pentene polymer (C) And the like are melt-kneaded. In the latter case, the 4-methyl-1-pentene polymer (C) is blended when the soft propylene composition (X) is produced from the soft propylene polymer (A) and the propylene polymer (B). This includes a form in which the propylene-based resin composition (Y) is obtained simultaneously with the production of the soft propylene composition (X).

The propylene-based resin composition (Y) of the present invention may contain other polymers as optional components within a range not impairing the object of the present invention. In that case, the blending amount is not particularly limited, but for example, 0.1 to 30 parts by weight with respect to 100 parts by weight of the soft propylene composition (X) in the propylene-based resin composition (Y) of the present invention. It is preferable that it is a grade.

  Preferred as such another polymer is an ethylene polymer or copolymer containing ethylene as a main component (51 mol% or more), and when these are blended, the flexibility of the propylene resin composition (Y) is obtained. And low temperature characteristics are improved.

  In addition, the propylene-based resin composition (Y) of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an antiblocking agent, an antifogging agent, and the like within a range not impairing the object of the present invention Additives such as a nucleating agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, an antioxidant, and a copper damage inhibitor may be blended as necessary.

  The molded body composed of the propylene-based resin composition (Y) of the present invention is a method for directly molding the propylene-based resin composition (Y), or when molding the soft propylene composition (X) of the present invention. Method of adding methyl-1-pentene polymer (C) (for example, when forming a propylene resin composition (Y) with a molding machine (extruder), from the middle of the molding machine (extruder) 4- It means a molded product obtained by feeding a methyl-1-pentene polymer (C). In addition, a preferred method for processing a molded article made of the propylene resin composition (Y) of the present invention is that the propylene resin composition (Y) is subjected to shearing and / or uniaxial, biaxial, and planar elongation flows in a molten state. There is no particular limitation as long as it is a known method, but specific examples of the molding method mainly involving shear flow include known molding methods such as extrusion molding, injection molding, and melt blown molding. Specific examples of the molding method mainly involving uniaxial, biaxial, and plane extension flow include known methods such as T-die (film) molding, blow molding, and stretching. Here, the molten state refers to a range from the melting point of the composition X to less than 350 ° C., preferably from 170 ° C. to 350 ° C.

  Since the soft propylene composition (X) of the present invention and the 4-methyl-1-pentene polymer (C) are not thermodynamically compatible, 4-methyl The -1-pentene polymer (C) component is considered to be localized. The molded product obtained by the effect of the 4-methyl-1-pentene polymer (C) having excellent heat resistance and low tackiness is suppressed in a sticky feeling under a wide environment from room temperature to high temperature.

  Preferable forms of the molded body comprising the propylene-based resin composition (Y) of the present invention include sheets, films, pipes or tubes, bottles, fibers, tapes, etc., and typical application examples using these are as follows. However, it is not limited to these.

  Cap liners, gaskets, glass interlayers, doors, door frames, window frames, edges, baseboards, opening frames, floor materials, ceiling materials, wallpaper, stationery, office supplies, anti-slip sheets, building material skin materials, pipes , Electric wire, sheath, wire harness, protective film adhesive layer, hot melt adhesive material, sanitary products, medical bags and tubes, non-woven fabric, elastic material, fiber, shoe sole, shoe midsole, inner sole, sole, sandals, for packaging Film, sheet, food packaging film (outer layer, inner layer, sealant, single layer), stretch film, wrap film, tableware, retort container, stretched film, breathable film.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the present invention and the following examples, the physical properties of the polymer or composition were measured as follows.
[Composition ratio of each comonomer]
^It was determined by analysis of ¹³ C-NMR spectrum.
[B value]
It was determined by analysis of ¹³ C-NMR spectrum according to the method described in JP-A-2007-186664.
[Stereoregularity (mm or mmmm)]
^It was determined by analysis of ¹³ C-NMR spectrum.

The isotactic triad fraction (mm) was determined by the method described from page 21 line 7 to page 26 line 6 of the pamphlet of International Publication No. 2004-087775.
The isotactic pentad fraction (mmmm) is disclosed in the prior publication (Japanese Patent Laid-Open No. 2003-147).
No. 135)).
[Molecular weight distribution]
GPC (gel permeation chromatography) was used as an orthodichlorobenzene solvent (mobile phase) and measured at a column temperature of 140 ° C. (polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight). Specifically, the molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 model manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL.The column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C, and the mobile phase is Using o-dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, it was moved at 1.0 ml / min, the sample concentration was 15 mg / 10 ml, and the sample injection volume was 500 A microliter was used, and a differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 106, and that of Pressure Chemical Co. was used for 1000 ≦ Mw ≦ 4 × 106.
[Melting point, glass transition temperature]
An exothermic / endothermic curve of DSC was obtained, and the temperature at the maximum melting peak position at the time of temperature rise was defined as Tm. The sample is packed in an aluminum pan, (i) heated to 200 ° C. at 100 ° C./min and held at 200 ° C. for 5 minutes, (ii) lowered to −50 ° C. at 20 ° C./min, (Iii) The temperature was raised to 200 ° C. at 20 ° C./min, and the obtained endothermic curve was analyzed and determined.
[Shore A hardness]
Using a hydraulic hot press molding machine set at 190 ° C. (using a 100 μm Lumirror (PET film) as a release film at the time of press molding), after heating for 5 minutes and molding in 2 minutes under 10 MPa pressure, 20 Using a sheet having a predetermined thickness obtained by cooling at 10 ° C. under a pressure of 10 MPa for 4 minutes, the scale was read immediately after contact with the push needle using an A-type measuring instrument after 72 hours at room temperature after molding. (Conforms to ASTM D-2240). For the soft propylene polymer (A) and the soft propylene composition (X), a sheet having a thickness of 2 mm was used, and for the propylene-based resin composition (Y), a sheet having a thickness of 1 mm described in Examples was used.
[Melt flow rate (MFR)]
Based on ASTM D-1238, MFR at 190 ° C. or 230 ° C. and 2.16 kg load was measured.
[Transparency (internal haze, total haze, light transmittance)]
For the soft propylene composition (X), a sheet having a thickness of 2 mm is used. For the propylene-based resin composition (Y), a sheet having a thickness of 1 mm described in the examples is used, and manufactured by Nippon Denshoku Industries Co., Ltd. The turbidity transmitted light amount and the total transmitted light amount were measured in a cyclohexanol solution using a digital turbidimeter “NDH-2000” and a C light source, and haze was calculated by the following equation.

Internal haze = 100 × (diffuse transmitted light amount) / (total transmitted light amount)
Total haze = 100 × (diffuse transmitted light amount) / (total transmitted light amount)
Total light transmittance = 100 × (total transmitted light amount) / (incident light amount)
[Intrinsic viscosity]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. Repeat this dilution operation two more times,
The value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0 [molecular weight])
[Critical surface tension]
Using an image processing type / solid-liquid interface analysis system (Dropmaster 500 manufactured by Kyowa Interface Science Co., Ltd.)
Under the atmosphere of 3 ° C. and 50% RH, four kinds of wet tension test mixed liquids (ethylene glycol monoethyl ether / formamide, surface tension of 31, 34, 37, 40 mN each having a known surface tension on the surface of the test sample. / M) was dropped and the contact angle was measured. The measurement was performed on five test samples, and the average value was obtained. The points (five or more) obtained from cos θ (Y axis) calculated from the contact angle θ and the surface tension (X axis) of the test liquid mixture are plotted on the XY coordinates, and the minimum of these points is plotted. The surface tension (X axis) corresponding to the intersection of the straight line obtained by the square method and cos θ = 1 was defined as the critical surface tension (mN / m).

In addition, adjustment of the test sample for critical surface tension measurement was as follows, and each critical surface tension was measured.
For the 4-methyl-1-pentene polymer, a 4-methyl-1-pentene polymer was cast on a SUS plate. Casting was performed by heating and melting a 4-methyl-1-pentene polymer on a SUS plate under a condition of 250 ° C. × 5 min in a nitrogen atmosphere, and then returning to normal temperature and solidifying. The critical surface tension of the surface of this test sample was measured.

About the film sample, the critical surface tension was measured about the chill roll surface side at the time of film forming.
[Terminal double bond]
The terminal double bond of the 4-methyl-1-pentene polymer in the present invention is:
It is classified into double bonds of vinyl type, vinylidene type, disubstituted internal olefin type and trisubstituted internal olefin type, and the total amount is measured by 1H-NMR.

  When the 4-methyl-1-pentene polymer is measured by 1H-NMR, the peak for 2 protons (H1) is around 4.8 to 5.0 ppm among the peaks for 3 protons derived from the vinyl group. The remaining one proton (H1 ′) is observed in the vicinity of 5.7 to 5.9 ppm.

Further, a peak (H2) for two protons derived from the vinylidene group is observed in the vicinity of 4.7 ppm.
Furthermore, the peak (H3) for two protons derived from the 2-substituted internal olefin is near 5.2 to 5.4 ppm, and the peak (H4) for 1 proton derived from the 3-substituted internal olefin is 5.0 to 5.2 ppm. Observed nearby.

When the integral value of all protons is Ha, the terminal double bond amount L (number / 1000 carbons) is L = [2 × (H1 + H1 ′) + 3 × (H2 + H3) + 6 × H4] × 1000 / Calculated from 3Ha.

^{For 1} H-NMR, a 20 nm sample was completely dissolved in about 0.5 ml of deuterated o-dichlorobenzene in an NMR sample tube (5 mmφ) using a JNM-ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL. , Measured at 120 ° C.
[Tackiness]
First, an extruded sheet (thickness 1 mm) formed by the method described in the examples was cut into a length (MD direction) of 120 mm and a width of 12.7 mm to obtain a sample. A set of test bodies obtained by superimposing the samples on the same surface was applied with a load of 2.5 kgf for 24 hours (treatment temperature = 23 ° C., 50 ° C.). After removing the load and allowing to stand at 23 ° C. for 1 day, these peeling forces were measured (T peel, peeling speed = 200 mm / min).
[Synthesis Example 1] Synthesis of soft propylene polymer (a-1) Ethylene 16.4 mol%, propylene 77.7 mol%, 1-butene 5.9 mol%, as a polymerization catalyst / co-catalyst as disclosed in JP-A-2007-186664 Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride / methylaluminoxane (Made by Tosoh Finechem) 0.3 mmol in terms of aluminum) was polymerized in a hexane solution using a continuous polymerization facility to obtain a soft propylene polymer (a-1) which is a propylene / ethylene / α-olefin copolymer. Table 1 shows the physical properties.
[Synthesis Example 2] Synthesis of Soft Propylene Polymer (a-2) The same procedure as in Synthesis Example 1 except that ethylene was 13.7 mol%, propylene 67.0 mol%, and 1-butene 19.3 mol%. A soft propylene polymer (a-2) which was an ethylene / α-olefin copolymer was obtained. Table 1 shows the physical properties.
[Synthesis Example 3] Synthesis of 4-methyl-1-pentene polymer (c-1) [Preparation of catalyst solution]
Add 1 μmol of isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride to a glass flask thoroughly purged with nitrogen as a promoter. A catalyst solution was obtained by adding 0.5 mmol of hexane solution of MMAO (product name: MMAO-3A) manufactured by Tosoh Finechem Co. in terms of Al atom.
[polymerization]
Dialene D168 (registered by Mitsubishi Chemical Corporation), which is a mixture of decane 561ml, 4-methyl-1-pentene 180ml, high-purity hexadecene and octadecene, in a glass autoclave with an internal volume of 1 liter, which is equipped with a stirrer and sufficiently purged with nitrogen (Trademark) (9 ml) was charged, hydrogen (6 liters / hour) was circulated, and the mixture was left at 30 ° C. for 10 minutes. Thereafter, 0.375 mmol of triisobutylaluminum and subsequently the catalyst solution prepared above were added to initiate polymerization. Hydrogen (6 liters / hour) was continuously supplied, polymerization was carried out at 30 ° C. under normal pressure for 1 hour, and then a small amount of methanol was added to stop the polymerization. The polymerization solution was poured into 4 liters of a methanol / acetone mixture (volume ratio 4/1), and the polymer was recovered by filtration. The obtained polymer was dried at 80 ° C. under reduced pressure for 10 hours to obtain 37.6 g of 4-methyl-1-pentene polymer (c-1). Table 1 shows the physical properties.
[Example 1]
90 parts by weight of the soft propylene polymer (a-1), isotactic homopolypropylene (b) as the propylene polymer (B) (Tm = 164 ° C., MFR (230 ° C.) = 7.0 g / 10 min, mmmm = 96.5%, Mw / Mn = 4.3) 10 parts by weight, and heat stabilizer (Irgaphos of Ciba Specialty Chemicals Co., Ltd. with respect to soft propylene polymer (a-1) and propylene polymer (B)) 168 of 500 ppm and Irganox 1076 of 500 ppm) were melt-kneaded at 190 ° C. to produce a soft propylene composition (x-
1) was obtained.
Furthermore, a 40 mmφ single screw extruder (L / D) was prepared by blending 1 part by weight of 4-methyl-1-pentene polymer (c-1) with 100 parts by weight of this soft propylene composition (x-1). = 26, a full flight screw) was melt kneaded (molding temperature = 230 ° C), and a 1 mmt extruded sheet molded body of the resin composition (y1) was molded, and the physical properties were measured. Table 1 shows the physical properties.
[Example 2]
Instead of 90 parts by weight of the soft propylene polymer (a-1), the same as in Example 1 except that 85 parts by weight of the soft propylene polymer (a-2) and 15 parts by weight of the propylene polymer (b) were used. Then, an extruded sheet molded body of 1 mmt of the resin composition (y2) was molded, and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 1]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-1)
) Was not blended, and a 1 mmt extruded sheet molded body of the resin composition (y3) was molded in the same manner as in Example 1, and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 2]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-1)
) In place of 1 part by weight of polypropylene wax (Mitsui Chemicals, brand name NP505, melting point = 151 ° C., melt viscosity (180 ° C.) = 650 mPa · s). A 1 mmt extruded sheet molded body of the resin composition (y4) was molded and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 3]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-1)
)) In the same manner as in Example 1 except that 1 part by weight of polyethylene wax (Mitsui Chemicals, brand name 420P, melting point = 113 ° C., melt viscosity (180 ° C.) = 650 mPa · s) was blended. A 1 mmt extruded sheet molded body of the resin composition (y5) was molded and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 4]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-1)
) Instead of erucic acid amide (manufactured by NOF Corporation, Alfro P-10) 1500pp
Except that m (0.15 parts by weight) was blended, a 1 mmt extruded sheet molded body of the resin composition (y6) was molded in the same manner as in Example 1, and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 5]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-2)
) Was not blended, and a 1 mmt extruded sheet molded body of the resin composition (y7) was molded in the same manner as in Example 2, and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 6]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-2)
) In place of 1 part by weight of polypropylene wax (Mitsui Chemicals, brand name NP505, melting point = 151 ° C., melt viscosity (180 ° C.) = 650 mPa · s). A 1 mmt extruded sheet molded body of the resin composition (y8) was molded and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 7]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-2)
)) In the same manner as in Example 2 except that 1 part by weight of polyethylene wax (Mitsui Chemicals, brand name 420P, melting point = 113 ° C., melt viscosity (180 ° C.) = 650 mPa · s) was blended. A 1 mmt extruded sheet molded body of the resin composition (y9) was molded, and the physical properties were measured. Table 1 shows the physical properties.
[Comparative Example 8]
4-methyl-1-pentene polymer (c-1) with respect to the soft propylene composition (x-2)
) Instead of erucic acid amide (manufactured by NOF Corporation, Alfro P-10) 1500pp
Except that m (0.15 parts by weight) was blended, a 1 mmt extruded sheet molded body of the resin composition (y10) was molded in the same manner as in Example 2, and the physical properties were measured. Table 1 shows the physical properties.

The propylene resin composition (Y) comprising the soft propylene composition (X) and the 4-methyl-1-pentene polymer (C) according to the present invention, at room temperature to high temperature without greatly impairing flexibility and transparency. Thus, it is possible to obtain a molded product in which stickiness is suppressed in a wide range of environments.
The technology of the present invention can be applied to various extrusion molded products, injection molded products, etc., and among them, it is preferable to apply to films, sheets, hollow molded products (tubes / hoses, bottles), fibers and the like.

Claims (8)

The soft propylene composition (X) comprising 60 to 100 parts by weight of the soft propylene polymer (A) and 0 to 40 parts by weight of the propylene polymer (B) (however, the sum of the components (A) and (B) is 100 parts by weight) and 0.1 to 15 parts by weight of the 4-methyl-1-pentene polymer (C), and the soft propylene polymer (A) includes the following (A1) to (A3):
(A1) Shore A hardness is in the range of 20-94.
(A2) The structural unit derived from propylene is 51 to 100 mol%.
(A3) Melting point observed by DSC is less than 100 ° C. or not observed,
The filling,
The propylene polymer (B) is the following (B1)
(B1) The melting point observed by DSC is in the range of 100 ° C. or more and less than 175 ° C.,
The filling,
And the 4-methyl-1-pentene polymer (C) is the following (C1):
(C1) The intrinsic viscosity [η] measured at 135 ° C. in a delican solvent is in the range of 0.01 dl / g or more and less than 0.50 dl / g.
A propylene-based resin composition (Y) characterized by satisfying The soft propylene polymer (A) is the following (A4) and (A5)
(A4) Propylene and ethylene containing 51 to 90 mol% of propylene-derived structural units, 0 to 49 mol% of ethylene-derived structural units, and 0 to 49 mol% of structural units derived from α-olefins having 4 to 20 carbon atoms Or a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, or a copolymer of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms (where propylene-derived structural units and The total of the structural unit derived from ethylene and the structural unit derived from α-olefin having 4 to 20 carbon atoms is 100 mol%),
(A5) The isotactic triad fraction (mm) calculated by ¹³ C-NMR is 85-99.9%.
And the propylene polymer (B) is (B2)
(B2) The isotactic pentad fraction (mmmm) calculated by ¹³ C-NMR is 90 to 99.8%.
The propylene-based resin composition (Y) according to claim 1, wherein: The soft propylene polymer (A) has the following (A6) to (A8):
(A6) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 1.2.
(A7) B value specified below is 0.8 to 1.3,

(In the formula, M _OE represents the molar fraction of the total of the chain of propylene and ethylene and the chain of α-olefin and ethylene having 4 or more carbon atoms to all dyads, and M 2 _O represents propylene and carbon atoms of 4 carbon atoms.
The total of the mole fractions of the above α-olefins is represented, and M _E represents the mole fraction of ethylene. )
(A8) Glass transition temperature (Tg) measured by DSC is observed in the range of −10 ° C. to −50 ° C.
The propylene-based resin composition (Y) according to claim 1 or 2, wherein: The soft propylene composition (X) is the following (X1) and (X2)
(X1) Shore A hardness is 20 to 94,
(X2) The internal haze of the 2 mmt press sheet is 0.1 to 15% and the total light transmittance is 80 to 99.9%.
The propylene-based resin composition (Y) according to any one of claims 1 to 3, wherein: The 4-methyl-1-pentene polymer (C) is the following (C2) to (C5):
(C2) The structural unit derived from 4-methyl-1-pentene is 50 to 100% by weight, and at least one or more selected from olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene. The total of structural units derived from the olefins is a 4-methyl-1-pentene polymer having 0 to 50% by weight,
(C3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 5.0.
(C4) The melting point (Tm) measured with a differential scanning calorimeter is in the range of 120 to 245 ° C.
(C5) The critical surface tension is in the range of 22-28 mN / m.
The propylene-based resin composition (Y) according to any one of claims 1 to 4, wherein: The 4-methyl-1-pentene polymer (C) is the following (C6):
(C6) satisfying the relationship of the following formula (I):
A ≦ 0.2 × [η] ^(-1.5) (I)
(In the above formula (I), A is a component having a polystyrene-reduced molecular weight of 1,000 or less in the 4-methyl-1-pentene polymer when measured by gel permeation chromatography (GPC). And [η] is the intrinsic viscosity (dl / g) measured at 135 ° C. in a delican solvent of the 4-methyl-1-pentene polymer.)
The propylene-based resin composition (Y) according to any one of claims 1 to 5, wherein: The 4-methyl-1-pentene polymer (C) is the following (C7):
(C7) The amount of terminal double bonds in the 4-methyl-1-pentene polymer calculated by ¹ H-NMR is 0.001 or more and 1000 or less per 1000 carbons,
The propylene-based resin composition (Y) according to any one of claims 1 to 6, wherein   A molded product obtained by shearing and / or uniaxially, biaxially, and planarly extending flow of the propylene-based resin composition (Y) according to claim 1 in a molten state.