JP2020122145A - Propylene-based resin composition - Google Patents

Abstract

SOLUTION: A propylene-based resin composition comprises a propylene-based resin (α), an olefin-based resin (β) satisfying specific requirements and an olefin-based resin (γ) satisfying specific requirements. The olefin-based resin (β) includes a graft-type olefin-based polymer [R1] having a main chain composed of an ethylene/α-olefin copolymer and a side chain composed of a propylene polymer. The olefin-based resin (γ) is an ethylene/α-olefin copolymer.EFFECT: A propylene-based resin composition according to the present invention is excellent in balance between rigidity and impact resistance and can be widely and suitably used for various products such as automobile parts, food containers and medical containers even though the amount used of a block polymer in which an ethylene-based copolymer and a propylene polymer are bonded is reduced than a conventional resin composition.SELECTED DRAWING: None

Description

The present invention relates to a propylene resin composition containing a specific olefin resin. More specifically, the present invention relates to a propylene-based resin composition capable of obtaining a molded product having an excellent balance of rigidity and impact resistance.

Among olefin resins, propylene resin is used in various fields such as daily sundries, kitchen appliances, packaging films, home electric appliances, mechanical parts, electric parts, and automobile parts, and various types are used according to the required performance. A propylene resin composition containing the above additive is used. Also, as an approach to 3R (Reduce, Reuse, Recycle) to form a recycling-based society, weight reduction by thin-walled molded products has been recently attempted in each industrial field. Improvements in propylene-based resin compositions are being made so that sufficient rigidity and impact resistance can be obtained even if the molded product is made lighter and thinner.

A polypropylene block copolymer is industrially produced as a polypropylene having improved impact resistance and is widely used for the above-mentioned applications. This block copolymer is also called an impact copolymer or a heterophasic copolymer. That is, in a multi-stage polymerization process, following homopolymer polymerization, ethylene is copolymerized in a subsequent reaction vessel to produce a composition containing an ethylene-propylene polymer. The term "block" of this polypropylene block copolymer does not mean "block copolymer". That is, the polypropylene block copolymer does not mean that the homopolypropylene chain and the ethylene-propylene copolymer chain are chemically bonded, and can be said to be a two-stage polymerization composition. Since the block copolymer produced in this way has a structure (sea-island structure) in which "islands" of ethylene-propylene polymer float in the "sea" of homopolymer, it is more resistant to propylene homopolymer. Although excellent in impact strength, from the above viewpoint, further improvement in the balance between rigidity and impact resistance has been desired.

Against this background, technological development of block polymers (including straight-chain type and branched type) in which an ethylene-based copolymer and a propylene polymer are actually bonded, which is excellent in polypropylene resin modification performance, is underway ( Patent Documents 1 to 4). For example, in Patent Document 4, by blending a graft-type polymer having a main chain of an ethylene/α-olefin copolymer chain and a side chain of a propylene polymer chain as a modifier with a propylene resin, It has been shown that a propylene-based resin composition having dramatically improved impact resistance can be obtained.

However, the block copolymer in which the ethylene copolymer and the polypropylene are bonded as described above is high in cost because the production process is complicated as compared with the usual ethylene copolymer, and the propylene resin composition using the same is used. Since the manufacturing cost of the product also becomes high, there was an economic problem.

JP, 2009-102598, A JP, 2009-227898, A Japanese Patent Publication No. 2013-527705 International Publication No. 2016/093266

The problem to be solved by the present invention is to provide a propylene-based resin composition having an excellent balance between rigidity and impact resistance, and further to provide a propylene-based resin composition with high economic rationality.

As a result of intensive studies to solve the above problems, the present inventors have found that a graft type olefin-based polymer having a main chain composed of an ethylene/α-olefin copolymer and a side chain composed of a propylene polymer is contained, It was found that a propylene-based resin composition containing the olefin-based resin satisfying the above requirement and an olefin-based resin comprising an ethylene/α-olefin copolymer satisfying the specific requirements can solve the above-mentioned problems.

That is, the present invention relates to the following.
[1] Propylene resin (α), olefin resin (β) satisfying the following requirements (β-I) to (β-VI), and olefin satisfying the following requirements (γ-I) to (γ-III). A propylene resin composition containing a resin (γ).
The (β-I) olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene/α-olefin copolymer and a side chain made of a propylene polymer.
(Β-II) When the proportion of the propylene polymer contained in the olefin resin (β) is Pwt%, P is in the range of 5 to 60.
(Β-III) The proportion of the component having a peak value of the differential elution curve of less than 65° C. measured by a cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent to the olefin resin (β) is Ewt%. Then, the value a represented by the following relational expression (Eq-1) is 1.4 or more.

（β−ＩＶ）示差走査熱量分析（ＤＳＣ）によって測定された融点（Ｔｍ）が１２０〜１６５℃の範囲にあり、ガラス転移温度（Ｔｇ）が−８０〜−３０℃の範囲にある。
（β−Ｖ）熱キシレン不溶解量が３ｗｔ％未満である。
（β−ＶＩ）１３５℃のデカリン中で測定した極限粘度［η］が０．５〜５．０ｄｌ／ｇの範囲にある。
（γ−Ｉ）前記オレフィン系樹脂（γ）は、エチレン・α−オレフィン共重合体である。
（γ−ＩＩ）示差走査熱量分析（ＤＳＣ）によって測定されたガラス転移温度（Ｔｇ）が−８０〜−３０℃の範囲にある。
（γ−ＩＩＩ）１３５℃のデカリン中で測定した極限粘度［η］が０．５〜５．０ｄｌ／ｇの範囲にある。
［２］ プロピレン系樹脂(α)とオレフィン系樹脂（β）とオレフィン系樹脂（γ）との含有量の合計を１００重量部としたとき、プロピレン系樹脂（α）の含有量が５０〜９０重量部であることを特徴とする［１］に記載のプロピレン系樹脂組成物。
［３］ オレフィン系樹脂（β）とオレフィン系樹脂（γ）との重量比（（β）／（γ））が９５／５〜５／９５の範囲にある［１］または［２］に記載のプロピレン系樹脂組成物。
［４］ オレフィン系樹脂（β）が 下記（Ａ）および（Ｂ）の工程を含む製造方法によって得られたものである、［１］〜［３］のいずれかに記載のプロピレン系樹脂組成物。
（Ａ）ジメチルシリルビスインデニル骨格を有する配位子を含む周期表第４族の遷移金属化合物［Ａ］を含むオレフィン重合用触媒の存在下でプロピレンを重合し、不飽和末端ポリプロピレンを製造する工程
（Ｂ）下記一般式［Ｂ］で表される架橋メタロセン化合物を含むオレフィン重合用触媒の存在下で、工程（Ａ）で製造される不飽和末端ポリプロピレンと、エチレンと、炭素原子数３〜２０のα−オレフィンから選ばれる少なくとも１種のα−オレフィンとを共重合する工程

(Β-IV) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165°C, and the glass transition temperature (Tg) is in the range of -80 to -30°C.
(Β-V) Thermal xylene insoluble amount is less than 3 wt %.
(Β-VI) The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 0.5 to 5.0 dl/g.
(Γ-I) The olefin resin (γ) is an ethylene/α-olefin copolymer.
(Γ-II) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30°C.
(Γ-III) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 5.0 dl/g.
[2] When the total content of the propylene resin (α), the olefin resin (β) and the olefin resin (γ) is 100 parts by weight, the content of the propylene resin (α) is 50 to 90. The propylene-based resin composition according to [1], which is parts by weight.
[3] The weight ratio ((β)/(γ)) of the olefin resin (β) and the olefin resin (γ) is in the range of 95/5 to 5/95, and is described in [1] or [2]. The propylene resin composition of.
[4] The propylene resin composition according to any one of [1] to [3], wherein the olefin resin (β) is obtained by a production method including the following steps (A) and (B). ..
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce an unsaturated terminal polypropylene. Step (B) In the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the following general formula [B], the unsaturated terminal polypropylene produced in step (A), ethylene, and 3 to 3 carbon atoms. Copolymerizing with at least one α-olefin selected from 20 α-olefins

（式［Ｂ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。

(In the formula [B], each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group or a silicon-containing group. A hetero atom-containing group is shown, and two adjacent groups of R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom and a hydrocarbon. The same atom or the same group selected from a group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may combine with each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.

Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anion ligand or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

The propylene resin composition according to the present invention has a balance between rigidity and impact resistance, although the amount of the block copolymer in which the ethylene copolymer and the propylene polymer are bonded is reduced as compared with the conventional resin composition. Excellent in. Therefore, the propylene-based resin composition according to the present invention is highly economically rational and can be widely and suitably used for various products such as automobile parts, food containers, and medical containers.

FIG. 1 is a graph showing the effect of modifying the impact resistance of the propylene resin composition of the present invention at room temperature by the balance between tensile elastic modulus and high-speed impact strength in the comparison between Examples and Comparative Examples. is there. FIG. 2 shows the effect of modifying the impact resistance at low temperature of the propylene-based resin composition of the present invention by comparing the Izod impact strength at −40° C. and the tensile elastic modulus in the comparison between Example and Comparative Example. It is the graph shown. FIG. 3 is a graph showing the correlation between the ratio P, the ratio E, and the a value.

The propylene resin composition of the present invention is characterized by containing a propylene resin (α), an olefin resin (β) and an olefin resin (γ) as essential components. Hereinafter, the propylene resin (α), the olefin resin (β), and the olefin resin (γ) will be described.

<Propylene resin (α)>
The propylene-based polymer (α) is a homopolymer of propylene or is composed of a copolymer of propylene and at least one selected from ethylene and α-olefins having 4 to 20 carbon atoms. The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 2 -Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene , 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-. Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene. , 1-dodecene and the like. Among these, 1-butene, 1-pentene, 1-hexene, and 1-octene α-olefins can be preferably used.

The propylene-based resin (α) may be composed of a single polymer among the above polymers, or may be composed of a plurality of polymers. The propylene resin (α) is polymerized with a Ziegler-Natta catalyst or the like.

As the propylene-based resin (α), any commercially available propylene-based resin can be used without particular limitation. Examples of commercially available propylene-based resins include so-called homopolypropylene resins, random polypropylene resins and block polypropylene resins, preferably homopolypropylene resins and block polypropylene resins, and more preferably homopolypropylene resins.

The homopolypropylene resin is a resin which is substantially a homopolymer of propylene, is generally inexpensive and easy to manufacture, and is excellent in rigidity and surface hardness, but inferior in impact resistance and toughness. When a homopolypropylene resin is used as the propylene resin (α) in the propylene resin composition of the present invention, the rigidity of the homopolypropylene resin is excellent due to the olefin resin (β) and the olefin resin (γ) described later. Impact resistance and toughness can be significantly improved while maintaining the characteristics.

Hereinafter, preferred embodiments of the propylene resin (α) will be described. The propylene-based resin (α) preferably has a melt flow rate (MFR) measured at 230° C. and a load of 2.16 kg according to ASTM D1238 of 0.1 to 500 g/10 minutes, and the lower limit of MFR. The value is preferably 0.2 g/10 min, more preferably 0.3 g/10 min, and the upper limit is preferably 300 g/10 min, more preferably 100 g/10 min, particularly preferably 50 g/10 min. .. When the MFR of the propylene-based resin (α) is less than 0.1 g/10 minutes, the fluidity may be low and a problem may occur in moldability. When the MFR of the propylene-based resin (α) is larger than 500 g/10 minutes, the strength of the propylene-based resin (α) itself may be low, and the mechanical strength of the obtained resin composition may be low.

MFR serves as an index of the molecular weight of the propylene-based resin (α), and the propylene-based resin (α) further preferably has a weight average molecular weight in terms of polypropylene calculated by gel permeation chromatography (GPC) of 80,000 to 900,000. , More preferably 100,000 to 700,000, and particularly preferably 150,000 to 700,000.

Furthermore, the propylene-based resin (α) preferably has a tensile elastic modulus of 500 to 3000 MPa, more preferably 600 to 2500 MPa, and even more preferably 650 to 2200 MPa. The tensile elastic modulus is a value measured at 23° C. on a press sheet having a thickness of 2 mm in accordance with JIS K7113-2. When the propylene-based polymer (α) has a tensile elastic modulus in the above range, the propylene-based resin composition containing the propylene-based polymer (α) has high rigidity and high hardness.

The propylene-based resin (α) is different from the propylene polymer contained in the olefin-based resin (β) described later. The terminal structure of the propylene resin (α) is substantially a saturated hydrocarbon, and specifically, the ratio of unsaturated terminals in the propylene resin (α) is usually less than 0.1 per 1000 carbon atoms.

<Olefin resin (β)>
The olefin resin (β) according to the present invention may be composed of only one kind of olefin polymer or may be composed of two or more kinds of olefin polymers, but the following requirement (β- It is characterized by satisfying all of I) to (β-VI).
The (β-I) olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene/α-olefin copolymer and a side chain made of a propylene polymer.
(Β-II) When the proportion of the propylene polymer contained in the olefin resin (β) is Pwt%, P is in the range of 5 to 60.
(Β-III) The ratio of the component having a peak temperature of the differential elution curve measured by cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent of less than 65° C. to the olefin resin (β) is Ewt%. Then, in E and P, the value a represented by the following relational expression (Eq-1) is 1.4 or more.

（β−ＩＶ）示差走査熱量分析（ＤＳＣ）によって測定された融点（Ｔｍ）が１２０〜１６５℃の範囲にあり、ガラス転移温度（Ｔｇ）が−８０〜−３０℃の範囲にある。
（β−Ｖ）熱キシレン不溶解量が３ｗｔ％未満である。
（β−ＶＩ）１３５℃のデカリン中で測定した極限粘度［η］が０．５〜５.０ｄｌ／ｇの範囲にある。

(Β-IV) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165°C, and the glass transition temperature (Tg) is in the range of -80 to -30°C.
(Β-V) Thermal xylene insoluble amount is less than 3 wt %.
(Β-VI) The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 0.5 to 5.0 dl/g.

Hereinafter, these requirements (β-I) to (β-VI) will be specifically described.
[Requirements (β-I)]
The olefin resin (β) contains the graft type olefin polymer [R1] as an essential constituent component. The graft type olefin polymer [R1] is a graft copolymer having a main chain composed of an ethylene/α-olefin copolymer and a side chain composed of a propylene polymer.
In the present invention, the term "graft copolymer" is a polymer in which one or more side chains are bonded to the main chain.

The graft type olefin polymer [R1] has a structure in which a side chain made of a propylene polymer is chemically bonded to a main chain made of an amorphous or low crystalline ethylene/α-olefin copolymer. The olefin-based resin (β) containing the graft-type olefin-based polymer [R1] exhibits higher compatibility than the ethylene/α-olefin copolymer propylene-based resin. Therefore, the propylene resin composition containing the olefin resin (β) can exhibit an extremely excellent balance of physical properties.

The graft type olefin polymer [R1] is a graft copolymer having a main chain and side chains as described above. In the present invention, the main chain and side chain of the graft type olefin polymer [R1] preferably satisfy the following requirements (i) to (iv).
(I) The main chain comprises a repeating unit derived from ethylene and a repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and derived from the α-olefin. The ratio of such units is in the range of 10 to 50 mol% with respect to all the repeating units contained in the main chain.
(Ii) The main chain is derived from an ethylene/α-olefin copolymer having a weight average molecular weight of 10,000 to 200,000.
(Iii) The side chain consists essentially of a repeating unit derived from propylene.
(Iv) The side chain is derived from a propylene polymer having a weight average molecular weight of 5,000 to 100,000.
Hereinafter, these requirements (i) to (iv) will be specifically described.

[Requirement (i)]
The main chain of the graft type olefin polymer [R1] is composed of an ethylene/α-olefin copolymer, and in the graft type olefin polymer [R1], flexibility, low temperature characteristics required as a modifier, etc. It will be the part responsible for the characteristics. In order to ensure such properties, the main chain of the graft-type olefin polymer [R1] has a repeating unit derived from ethylene and at least one α selected from α-olefins having 3 to 20 carbon atoms. -Comprising repeating units derived from olefins.

Specific examples of the C3-C20 α-olefin copolymerized with ethylene in the ethylene/α-olefin copolymer include propylene, 1-butene, 2-methyl-1-propene, and 2-methyl. -1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene , 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl- 1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene , Diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like.

More preferred are α-olefins having 3 to 10 carbon atoms, and even more preferred are α-olefins having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Examples thereof include branched olefins such as 3-methyl-1-butene, and among them, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, 1-butene, 1-pentene and 1-hexene. , 1-octene is more preferred. By using 1-butene, 1-pentene, 1-hexene, or 1-octene as the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene, a propylene-based resin composition having the best physical property balance can be obtained. To be

The proportion of repeating units derived from ethylene in the main chain of the graft type olefin polymer [R1] is 50 to 90 mol%, preferably 60 to 90 mol%, and more preferably 70% based on the total repeating units contained in the main chain. ˜90 mol %, and even more preferably 75 to 85 mol %. The proportion of repeating units derived from α-olefin is 10 to 50 mol%, preferably 10 to 40 mol%, more preferably 10 to 30 mol%, and even more preferably 15 to 25 mol based on all repeating units contained in the main chain. % Range.

The relationship between the proportion of repeating units derived from ethylene and the α-olefin and the glass transition temperature (Tg) varies depending on the type of the α-olefin used, but the glass transition temperature (Tg) of the requirement (β-IV) is In order to achieve the range, the proportion of repeating units of ethylene and α-olefin in the main chain of the graft type olefin polymer [R1] is preferably in the above range.

When the proportion of repeating units derived from ethylene and α-olefin in the main chain is within the above range, the olefin resin (β) has excellent flexibility, and the phase with the olefin resin (γ) described below is further improved. The propylene-based resin composition is excellent in impact resistance and elongation property because it has good solubility and can improve the dispersion state.

On the other hand, when the repeating unit derived from α-olefin is less than 10 mol%, the obtained olefin resin has poor flexibility, and thus the propylene resin composition containing the resin has poor impact resistance and elongation property. There are cases.

The molar ratio of repeating units derived from ethylene and α-olefin in the main chain is controlled by controlling the ratio between the concentration of ethylene and the concentration of α-olefin present in the polymerization reaction system in the step of producing the main chain. Can be adjusted.

The molar ratio (mol%) of repeating units derived from the α-olefin contained in the main chain, that is, the α-olefin composition in the main chain is obtained, for example, under the condition that the terminal unsaturated polypropylene described below is not included. It can be obtained by obtaining the α-olefin composition of the ethylene/α-olefin copolymer by a conventional method, or by subtracting the influence derived from the terminal unsaturated polypropylene or the side chain from the α-olefin composition of the olefin resin (β). ..

[Requirement (ii)]
The weight average molecular weight of the ethylene/α-olefin copolymer constituting the main chain of the graft type olefin polymer [R1] is in the range of 50,000 to 200,000. In the polypropylene resin composition of the present invention, in order to improve the moldability (fluidity) of the resin while maintaining the mechanical strength, the weight average molecular weight is preferably 100,000 to 200,000.

When the weight average molecular weight of the ethylene/α-olefin copolymer constituting the main chain of the graft type olefin polymer [R1] is within the above range, the propylene resin composition containing the olefin resin (β) is resistant to The balance of impact resistance, rigidity and toughness tends to be better. On the other hand, when the weight average molecular weight is less than 50,000, impact resistance and toughness are deteriorated, and when the weight average molecular weight is more than 200,000, poor dispersion in propylene-based resin occurs and it may be difficult to obtain a desired balance of physical properties.

The weight average molecular weight of the ethylene/α-olefin copolymer constituting the main chain of the graft type olefin polymer [R1] can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described later. Examples of methods for controlling the ethylene concentration include ethylene partial pressure adjustment and polymerization temperature adjustment. The weight average molecular weight of the ethylene/α-olefin copolymer constituting the main chain can be adjusted by supplying hydrogen into the polymerization system.

The weight average molecular weight is a polyethylene equivalent weight average molecular weight determined by gel permeation chromatography (GPC). The weight average molecular weight of the ethylene/α-olefin copolymer constituting the main chain is, for example, by analyzing the ethylene/α-olefin copolymer when produced under the condition not containing the terminal unsaturated polypropylene described later or , The olefin resin (β) is analyzed and the influence derived from the terminal unsaturated polypropylene or the side chain is subtracted.

[Requirements (iii)]
The side chain of the graft type olefin polymer [R1] is substantially composed of a repeating unit derived from propylene. The side chain of the graft type olefin polymer [R1] is a propylene polymer having isotactic regularity which is substantially composed of repeating units derived from propylene.

The propylene polymer substantially composed of repeating units derived from propylene preferably has a molar ratio of repeating units derived from propylene of 99.5 to 100 mol% based on all repeating units contained in the propylene polymer. A polymer is shown. That is, a small amount of α-olefin other than ethylene and propylene may be copolymerized within a range that does not impair its role and characteristics.

More preferably, the side chain of the graft type olefin polymer [R1] is a propylene polymer chain having an isotactic pentad fraction (mmmm) of 85% or more, more preferably 90% or more.

Since the side chain of the graft type olefin polymer [R1] has the above characteristics, the side chain exhibits crystallinity and has a melting point. When the side chain of the graft type olefin polymer [R1] is a high melting point isotactic polyprepropylene polymer, the compatibility of the olefin resin (β) with the propylene resin is enhanced. Therefore, the resulting propylene-based resin composition has good rigidity and hardness while exhibiting good impact resistance.

The graft type olefin polymer [R1] is obtained by copolymerizing the terminal unsaturated polypropylene produced in the step (A) with ethylene and α-olefin in the step (B) for producing the olefin resin (β) described below. Can be obtained by That is, the composition and stereoregularity of the terminal unsaturated polypropylene correspond to the composition and stereoregularity of the side chain of the graft type olefin polymer [R1]. Therefore, the composition and stereoregularity of the terminally unsaturated polypropylene produced in the step (A) are calculated by using a known method, and the composition and stereoregularity are calculated based on the composition of the side chain of the graft-type olefin polymer [R1] and It can be defined as stereoregularity.

[Requirement (iv)]
The side chain is derived from a propylene polymer having a weight average molecular weight of 5,000 to 100,000. That is, the graft type olefin polymer [R1] has a structure in which a macromonomer, which is a propylene polymer having a weight average molecular weight of 5,000 to 100,000, is bonded to an ethylene/α-olefin copolymer, The merging site becomes the side chain. The weight average molecular weight is preferably 5,000 to 60,000, more preferably 5,000 to 25,000, and still more preferably 10,000 to 25,000.

When the weight average molecular weight of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is in the above range, the compatibility between the propylene polymer and the olefin resin (β) is increased and the propylene resin The impact resistance and the elongation property of the propylene-based resin composition containing the olefin resin (β) and the olefin resin (β) are well expressed, and the fluidity at the time of injection molding is also good.

If the weight average molecular weight of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is less than 5000, the interfacial strength with the propylene resin becomes weak, and the elongation and impact resistance of the propylene resin composition are reduced. May decrease.

When the weight average molecular weight of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is more than 100,000, the fluidity of the resin composition containing the olefin resin (β) at the time of molding is deteriorated, and processing is performed. May cause sexual deterioration. Further, the compatibility between the propylene resin and the olefin resin (β) is lowered, and the tensile elongation and impact resistance of the propylene resin composition containing the propylene resin and the olefin resin (β) are lowered. However, the surface hardness of the molded product obtained from the propylene-based resin composition may decrease.

The weight average molecular weight of the propylene polymer constituting the side chain is measured by a conventional method as in the above-mentioned "Requirement (iii)", in which the weight average molecular weight of the terminal unsaturated polypropylene produced in the step (A) is measured. You can ask for it. For example, the polypropylene-equivalent weight average molecular weight of the terminal unsaturated polypropylene obtained by gel permeation chromatography (GPC) can be used as the weight average molecular weight of the propylene polymer constituting the side chain.
Examples of the method for adjusting the weight average molecular weight of the propylene polymer constituting the side chain include a method for adjusting the polymerization temperature and the polymerization pressure in the production step (A) described below.

[Requirements (β-II)]
When the proportion of the propylene polymer contained in the olefin resin (β) (hereinafter, also referred to as proportion P) is Pwt%, P is in the range of 5 to 60%. Here, the propylene polymer contained in the olefin resin (β) means a polypropylene side chain incorporated into the main chain and a polypropylene linear polymer not incorporated into the main chain in the polymerization step (B) described later. The sum is shown.

The ratio P is preferably 8 to 50 wt%, more preferably 8 to 40 wt%, even more preferably 15 to 40 wt%, and even more preferably 20 to 35 wt%.
When the ratio P is in the above range, the compatibility between the propylene polymer and the olefin resin (β) is increased, and the impact resistance of the propylene resin composition containing the propylene polymer and the olefin resin (β) is increased. Good elongation at break. When the ratio P is less than 5, the compatibility with the propylene polymer is low, and the resulting propylene resin composition may not exhibit good physical properties in impact resistance and elongation at break. When the ratio P is greater than 60, the resulting propylene-based resin composition may not exhibit good physical properties in impact resistance and elongation at break due to the relatively small content of the ethylene/α-olefin copolymer. ..

The ratio P is obtained, for example, from the ratio of the weight of the terminal unsaturated polypropylene used in the polymerization step (B) described below to the weight of the obtained olefin resin (β).
Further, the terminal unsaturated polypropylene means polypropylene having an unsaturated terminal represented by the following terminal structures (I) to (IV). “Poly” in the terminal structures (I) to (IV) indicates the bonding position between the terminal structure and the propylene polymer molecular chain other than the terminal structure.

The ratio of unsaturated terminals in the terminal unsaturated polypropylene is usually 0.1 to 10 per 1000 carbon atoms, and more preferably 0.4 to 5.0. Further, the unsaturated terminal ratio represented by the terminal structure (I) generally called terminal vinyl is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.4 to 2 It is in the range of 0.

The quantification of the unsaturated terminal can be determined by determining the terminal structure of terminally unsaturated polypropylene by ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The terminal structure can be assigned according to the method described in Macromolecular Rapid Communications 2000, 1103 and the like.

For example, in the case of the terminal structure (I), if the integral value A of δ4.9 to 5.1 (2H) and the total integral value derived from the propylene polymer are B, the terminal structure (I) per 1000 carbon atoms The ratio is calculated by the formula 1000×(A/2)/(B/2). Also in the case of obtaining the ratio of other terminal structures, it may be replaced with the integrated value of the peak attributed to each structure while paying attention to the hydrogen ratio.

[Requirements (β-III)]
The olefin resin (β) is the proportion of components whose peak temperature of the differential elution curve measured by cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent is less than 65°C (hereinafter, also referred to as proportion E). When Ewt%, the value a represented by the following relational expression (Eq-1) (hereinafter, also referred to as a value) is 1.4 or more, preferably 1.6 or more, and more preferably 2.2 or more. Is.

The differential elution curve is obtained by differentiating the cumulative elution curve obtained in the elution temperature range of -20°C to 140°C. Further, by separating each elution peak appearing in the differential elution curve into a normal distribution curve, the component ratio of each elution peak can be obtained. Here, the ratio of soluble components below -20°C (the ratio of components not coated in the temperature rising elution fractionation (TREF) column even at -20°C in the cooling step of CFC measurement) is E _(<-20 °C ₎ wt. %, - the sum of the percentage of eluted component having a peak at less than 20 ° C. or higher _{65 ℃ E (<65 ℃)} wt%, the sum of the percentage of the eluted components having a peak at 140 ° C. or less 65 ° C. or more E _{(≧ 65} ℃ ₎ wt%, the proportion of components that do not dissolve at 140 ℃ is E _(>140 ℃ ₎ wt%, E _(<-20 ℃ ₎ +E _(<65 ℃ ₎ +E ₍ ≧ ₆₅ ℃ ₎ +E _(>140 ℃ ₎ =100 _Is defined as E=E _(<-20 ° C. ₎ +E _(<65 ° C. ₎ .

Usually, the olefin resin (beta) is the total amount soluble respect of 140 ° C. o-dichlorobenzene, because it can detect a clear peak is easily peak separation than 65 ° C., E of _{(> 140 ℃)} = 0 In this case, E=100−E ₍ ≧ ₆₅ ° C. ₎ is defined.

An infrared spectrophotometer (detection wavelength: 3.42 μm) is preferably used as the detector in the CFC measurement.
In addition, in the above-mentioned ratio E and ratio P to the total amount of the olefinic resin (β), the total amount is only for the resin obtained through the polymerization step described later, and the separately added resins and additives are the same as those described above. Not included in the total amount of.

The a value falling within the above range means that the olefin resin (β) is a graft type olefin polymer [R1], that is, an ethylene/α-olefin copolymer having a propylene polymer moiety as a side chain. It indicates that the amount is included.

FIG. 3 is a diagram showing the relationship between the ratio E (wt %), the ratio P (wt %) and the a value.
In FIG. 3, the dotted line showing the relationship of a=1 indicates the case where the graft type olefin polymer [R1] is not contained, that is, the case where the ethylene/α-olefin copolymer and the propylene polymer are mixed. On the other hand, the value of the ratio E with respect to the ratio P decreases as the production efficiency of the graft olefin polymer [R1] increases. As shown in FIG. 3, a large a value indicates that the graft-type olefin polymer [R1] has a high production efficiency. The olefin resin (β) of the present invention is characterized by having an a value of 1.4 or more.

Usually, a commercially available olefin-based elastomer used as a polypropylene resin modifier is composed of an ethylene/α-olefin copolymer (for example, an ethylene/butene copolymer or an ethylene/octene copolymer) and has a composition of ethylene. Is a polymer adjusted to about 90 mol% to 50 mol %. Therefore, the elution component ratio E of a normal ethylene/α-olefin copolymer is substantially 100%.

When an olefin-based elastomer composed of an ethylene/α-olefin copolymer is mixed with a propylene-based resin, the olefin-based elastomer is dispersed in the propylene-based resin and plays a role of imparting improvement in impact resistance. Increasing the amount of the olefin-based elastomer compounded improves the impact resistance, but on the other hand reduces the inherent rigidity and mechanical strength of the propylene-based resin. Therefore, generally, in a polypropylene resin composition, impact strength and rigidity are mutually opposite physical properties.

The olefin resin (β) contains a high content of a graft type olefin polymer [R1] in which a crystalline propylene polymer is chemically bonded to an ethylene/α-olefin copolymer. It is characterized in that E is small with respect to the content of the olefin copolymer.

When such an olefin resin (β) and an olefin resin (γ) described later are mixed with a propylene resin, the polypropylene side chain of the graft type olefin polymer [R1] has a good affinity with the propylene resin. As a result, it is considered that a phase separation structure in which an ethylene/α-olefin copolymer is finely dispersed in a propylene resin can be formed. At this time, at the interface between the ethylene/α-olefin copolymer and the propylene-based resin which are incompatible with each other, the polypropylene side chain of the graft-type olefin-based polymer [R1] becomes a crystal of the propylene-based resin. It is considered that it penetrates and exerts an effect of increasing the strength of the interface. Therefore, the propylene-based composition containing the olefin-based resin (β) containing a high content of the graft-type olefin-based polymer [R1] is excellent in rigidity, impact resistance and elongation physical properties, and is The balance of physical properties is also significantly improved.

[Requirements (β-IV)]
The olefin resin (β) has a melting point (Tm) measured by differential scanning calorimetry (DSC) of 120 to 165°C and a glass transition temperature (Tg) of -80 to -30°C. ..

Olefin resin (β) The melting point is preferably 130 to 160°C, more preferably 140°C to 160°C. That is, the olefin resin (β) has a melting peak measured by differential scanning calorimetry (DC) in the range of 120 to 165°C, preferably 130 to 160°C, more preferably 140°C to 160°C.

The temperature at which the above-mentioned melting peak appears, that is, the melting point (Tm) and the heat of fusion (ΔH) described later, is obtained by melting the sample once by the DSC by the temperature raising step and then crystallizing it by the cooling step up to 30°C. It is an analysis of an endothermic peak that appears in the temperature raising step (temperature raising rate of 10° C./min).

The melting point (Tm) and the heat of fusion (ΔH) observed in the above range are mainly due to the polypropylene side chain of the graft type olefin polymer [R1] constituting the olefin resin (β). When the melting point (Tm) is within the above range, and more preferably the heat of fusion (ΔH) is within the range described below, the olefin resin (β) has high compatibility with the propylene resin, and as a result, the olefin resin The propylene-based resin composition containing (β) has a good balance of rigidity, heat resistance, toughness, and the like. Examples of the method of adjusting the melting point (Tm) within the above range include a method of adjusting the polymerization temperature and the polymerization pressure in the production step (A) described below.

The glass transition temperature (Tg) of the olefin resin (β) is preferably −80 to −40° C., more preferably −70° C. to −50° C.
The glass transition temperature (Tg) is mainly due to the property of the ethylene/α-olefin copolymer of the main chain of the graft type olefin polymer [R1]. When the glass transition temperature (Tg) is in the range of −80° C. to −30° C., the propylene resin composition containing the olefin resin (β) exhibits good impact resistance.
The glass transition temperature (Tg) in the above range can be obtained by controlling the type and composition of the α-olefin of the ethylene/α-olefin copolymer.

[Requirements (β-V)]
The olefin-based resin (β) has a thermal xylene insoluble amount of less than 3.0 wt%, preferably less than 2.5 wt%, more preferably less than 2.0 wt%.

The thermal xylene insoluble amount is a value calculated by the following method.
The sample is heat-pressed (180° C., heating for 5 minutes, cooling for 1 minute) to form a sheet having a thickness of 0.4 mm and finely cut. About 100 mg of it is weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene in a closed container at 140° C. for 3 hours. Next, the screen is taken out and dried at 80° C. for 2 hours or more until a constant weight is obtained. The thermal xylene insoluble amount (wt%) is represented by the following equation.
Thermal xylene insoluble amount (wt%)=100×(W3-W2)/(W1-W2)
W1: total mass of screen and sample before test, W2: mass of screen, W3: total mass of screen and sample after test

As described above, the olefin resin (β) does not contain the amount of insoluble hot xylene at all, or contains a small amount, so that it can be well dispersed in the propylene polymer, and as a result, the desired effect is exhibited. To do. On the other hand, when the amount of the thermal xylene-insoluble portion is 3 wt% or more, the molded product obtained from the propylene-based resin composition may have a defective appearance called “pocket”.

As shown in the production method described later, by adopting a method of directly obtaining a graft type olefin polymer from the polymerization step, an olefin resin (β) having a thermal xylene insoluble component in the above range can be obtained.

[Requirements (β-VI)]
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.5 to 5.0 dl/g. The intrinsic viscosity [η] is preferably 1.0 to 4.0 dl/g, more preferably 1.0 to 3.0 dl/g. When the intrinsic viscosity [η] is in the above range, the propylene-based resin composition containing the olefin resin (β) has good rigidity and mechanical strength in addition to impact resistance, and further has good molding properties. It also has workability.
The olefin resin (β) preferably satisfies one or more of the following requirements (β-VII) to (β-XI) in addition to the above requirements (β-I) to (β-VI).

[Requirements (β-VII)]
The proportion of repeating units derived from ethylene in the entire olefin resin (β) is preferably 20 to 80 mol%, more preferably 30 to 80 mol, based on all repeating units contained in the olefin resin (β). %, more preferably 40 to 80 mol %, and particularly preferably 40 to 75 mol %. When the repeating unit derived from ethylene is in the above range, the olefin resin (β) is in a mode in which the ethylene/α-olefin copolymer is more contained, and the propylene resin containing the olefin resin (β) is included. The resin composition has good impact resistance and elongation at break.

[Requirements (β-VIII)]
The requirement (β-VIII) is that the elastic modulus is 200 MPa or less. The elastic modulus is more preferably 100 MPa or less, further preferably 50 MPa or less.
Since the olefin resin (β) contains the graft type olefin polymer [R1] and abundantly contains the ethylene/α-olefin copolymer moiety which is the main chain of the olefin resin (β), flexibility due to the copolymer moiety is present. have. When the elastic modulus of the olefin resin (β) is within the above range, the propylene resin composition containing the olefin resin (β) exhibits good impact resistance. The elastic modulus is a tensile elastic modulus according to ASTM D638.

[Requirements (β-IX)]
The requirement (β-IX) has a phase separation structure composed of a sea phase showing an amorphous component and an island phase showing a crystalline component, and the average diameter of the island phase in a transmission electron microscope image is 50 nm to 500 nm. It is in the range of. The average diameter of the island phase is more preferably 50 nm to 300 nm.

The observation as to whether or not it has the above-mentioned phase structure is performed as follows, for example.
First, an olefin resin is charged into a kneading and molding evaluation device, and melt-kneaded at 200° C. and 60 rpm for 5 minutes. Using an oil pressure type heat press molding machine set to 170° C., this olefin resin is preheated for 5 minutes, molded under pressure of 10 MPa for 1 minute, and then cooled at 20° C. under pressure of 10 MPa for 3 minutes. A press sheet having a predetermined thickness is produced by.

The above press sheet is cut into 0.5 mm square pieces and dyed with ruthenic acid (RuO ₄ ). Further, an ultramicrotome equipped with a diamond knife is used to cut the small pieces into ultrathin sections having a film thickness of about 100 nm. Carbon is vapor-deposited on this ultrathin section and observed with a transmission electron microscope (accelerating voltage 100 kV). The average particle size of the island phase can be obtained as the average major axis of the island phase by subjecting the obtained observed image to image processing and image analysis using commercially available image analysis software.

According to such an observation method, the propylene-based polymer component is observed as a higher contrast because the intercrystalline noncrystalline portion of the lamella structure formed by the component is selectively dyed with osninic acid.

In the phase separation structure of the olefin resin (β), the sea phase is formed from an amorphous or low crystalline ethylene/α-olefin copolymer, and the island phase is formed from a crystalline propylene polymer. It is a thing.

The fact that the ethylene/α-olefin copolymer becomes the sea phase indicates that the polymer component is present as the main component. This makes it possible to impart impact resistance to the propylene resin composition. Furthermore, the fact that the olefin resin (β) forms a very fine microphase-separated structure as described above means that the olefin resin (β) is compatible with the amorphous component or the low crystalline component and the crystalline component. It shows that the graft type olefin polymer [R1] which enhances the effect is contained in a high content. As a result, the physical property balance of the propylene resin composition containing the olefin resin (β) is remarkably excellent.

On the other hand, a resin which does not sufficiently contain an ethylene/α-olefin copolymer as a main component may not form a clear island phase due to a crystal component and may form a continuous phase. When such a resin is used, a resin composition having extremely poor impact resistance can be obtained. Further, in the case of a mere polymer blend of an ethylene/α-olefin copolymer and a propylene-based polymer or a resin which does not sufficiently contain the graft type olefin-based polymer [R1], the fine phase separation structure as described above is It is not formed and a coarse island phase is observed. When such a resin is used, the resulting propylene resin composition does not exhibit a good balance of physical properties.

[Requirements (β-X)]
The requirement (β-X) is that the heat of fusion ΔH at the melting peak (Tm) measured by differential scanning calorimetry (DSC) is in the range of 5 to 50 J/g. The heat of fusion ΔH is preferably in the range of 5 to 40 J/g, more preferably 10 to 30 J/g.

The melting peak (Tm) observed in the above range has a side chain composed of a propylene polymer of the graft type olefin polymer [R1] and a propylene polymer having an unsaturated terminal contained in the olefin resin (β). And the fact that the heat of fusion (ΔH) is observed in the above range means that the side chain moiety of the graft type olefin polymer [R1] contained in the olefin resin (β) is in a considerable amount. It indicates that it contains.

[Requirements (β-XI)]
The requirement (β-XI) is that the olefin resin (β) of the present invention has a proportion of ortho-dichlorobenzene-soluble components at 50° C. or less measured by cross fractionation chromatography (CFC) of 50 wt% or less. .. The ratio is preferably 40 wt% or less.
By satisfying the requirement (X) in addition to the requirement (III), the effect of including the graft-type olefin polymer [R1] is further enhanced.

It is preferable that the olefin resin (β) further contains no substance causing coloration, off-flavor, contamination of the final product and the like.
Specific examples of the substance that causes coloration, offensive odor, contamination of the final product, and the like include a compound containing a hetero atom, and the compound containing a hetero atom contains a halogen atom such as a chlorine atom or a bromine atom. Examples thereof include compounds, compounds containing chalcogen atoms such as acid atoms and sulfur atoms, and compounds containing pnictogen compounds such as nitrogen atoms and phosphorus atoms. Specific examples of the compound containing an oxygen atom include maleic anhydride and a maleic anhydride reaction product.

In addition, examples of the substance that causes the coloring, the offensive odor, the contamination of the final product, and the like include metal atom-containing compounds, specifically, alkali metal-containing compounds such as sodium and potassium, and alkaline earth compounds such as magnesium and calcium. Examples include metal-containing compounds.

The content of the heteroatom-containing compound in the olefin resin (β) is preferably 1000 ppm or less, more preferably 100 ppm or less, still more preferably 10 ppm or less. The content of the metal atom-containing compound in the olefin resin (β) is preferably 1000 ppm or less, more preferably 100 ppm or less, and further preferably 10 ppm or less.

<Method for producing olefin resin (β)>
The olefin resin (β) is preferably produced by a production method including the following steps (A) and (B), for example.
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce a terminally unsaturated polypropylene. Step (B) In the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound [B] represented by the following general formula [B], the terminal unsaturated polypropylene produced in step (A), ethylene, and a carbon atom. Step of copolymerizing with at least one α-olefin selected from α-olefins of several 3 to 20

（式［Ｂ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。

(In the formula [B], each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group or a silicon-containing group. A hetero atom-containing group is shown, and two adjacent groups of R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom and a hydrocarbon. The same atom or the same group selected from a group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may combine with each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.
M ¹ represents a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.

Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anion ligand or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )
Hereinafter, the steps (A) and (B) will be described in order.

[Step (A)]
The step (A) is a step of producing a terminal unsaturated polypropylene that is a raw material for the polypropylene side chain of the graft type olefin polymer [R1].
This step is a step of polymerizing propylene in the presence of a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce a terminally unsaturated polypropylene.

The unsaturated terminal of the terminal unsaturated polypropylene means the above-mentioned terminal structures (I) to (IV). The proportion of the terminal structure (I) in the unsaturated terminal is usually 30% or more, preferably 50% or more, more preferably 60% or more. The ratio of the terminal structure (I) among the unsaturated terminals is the sum of the numbers of the respective terminal structures (I) to (IV) present per 1000 carbon atoms contained in the terminal unsaturated polypropylene. To the ratio of the number of the terminal structure (I) present per 1000 carbon atoms to.

The transition metal compound [A] functions as a polymerization catalyst for producing terminally unsaturated polypropylene by combining with the compound [C] described below.
Examples of olefin polymerization catalysts for producing terminally unsaturated polypropylene include Resconi, L.; JACS 1992, 114, 1025-1032 and the like have been known for a long time, but as the side chain of the olefin copolymer [R1], isotactic or syndiotactic terminal unsaturated polypropylene, more preferably isotactic. Tick end unsaturated polypropylene is preferred.

The transition metal compound [A] contained in the olefin polymerization catalyst used for producing a polypropylene having such a high stereoregularity and a high terminal unsaturated polypropylene content having a terminal structure (I) is: The compounds disclosed in JP-A-6-100579, JP-A-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, and JP-A-2008-285443 can be preferably used.

More specific examples of the transition metal compound [A] include compounds selected from the group consisting of bridged bis(indenyl)zirconocenes or hafnocenes as a preferable example. More preferably, it is dimethylsilyl bridged bis(indenyl)zirconocene or hafnocene. More preferably, it is dimethylsilyl-bridged bis(indenyl)zirconocene, and by selecting zirconocene, generation of a long-chain branched polymer caused by an insertion reaction of terminal unsaturated polypropylene is suppressed, and an olefin resin (β) is contained. The propylene-based resin composition exhibits desired physical properties. On the other hand, when a large amount of the long chain branched polymer is produced in the step (A), the propylene resin composition containing the olefin resin (β) may impair the physical properties such as rigidity.

More specifically, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride or dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl can be used as a suitable compound.

The step (A) can be carried out by any of gas phase polymerization, slurry polymerization, bulk polymerization, and solution (dissolution) polymerization, and the polymerization form is not particularly limited.
When the step (A) is carried out by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, xylene. And aromatic hydrocarbons such as ethylene chloride, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used alone or in combination of two or more. Of these, hexane is preferable from the viewpoint of reducing the load of the post-treatment process.

The polymerization temperature in step (A) is usually 50°C to 200°C, preferably 80°C to 150°C, more preferably 80°C to 130°C, and the polymerization temperature should be controlled appropriately. Thus, it becomes possible to obtain a terminally unsaturated polypropylene having a desired molecular weight and stereoregularity.

The polymerization pressure in the step (A) is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction is carried out in any of a batch system, a semi-continuous system and a continuous system. It can be carried out. In the present invention, of these, it is preferable to employ the method of continuously supplying the monomer to the reactor to carry out the copolymerization.

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. Is.

The polymer concentration in the step (A) is 5 to 50 wt %, preferably 10 to 40 wt% in the steady operation. From the viewpoint of the viscosity limit in the polymerization ability, the load of the post-treatment process (desolvation) and the productivity, it is preferably 15 to 50 wt %.

The weight average molecular weight of the terminally unsaturated polypropylene produced in the step (A) is preferably in the range of 5,000 to 100,000, more preferably 5,000 to 60,000, and even more preferably 5,000 to 25,000. By the terminal unsaturated polypropylene having the weight average molecular weight in the above range, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin in the step (B) described later. The efficiency of introduction into the chain is high. On the other hand, when the amount exceeds the above range, the molar concentration of the terminally unsaturated polypropylene becomes relatively low, and the introduction efficiency into the main chain becomes low. Further, if it is less than the above range, there is a practical problem such as a decrease in melting point.

The molecular weight distribution (Mw/Mn) of the terminally unsaturated polypropylene produced in the step (A) is 1.5 to 3.0, typically about 1.7 to 2.5. In some cases, a mixture of side chains having different molecular weights may be used.

The ratio of unsaturated terminals measured by ¹ H-NMR of the terminally unsaturated polypropylene produced in the step (A) is usually 0.1 to 10 per 1000 carbon atoms, but more preferably 0.4 to It is 5.0. Further, the proportion of unsaturated terminals having a terminal structure (I), the so-called terminal vinyl amount, is usually 0.1 to 2.0 per 1000 carbon atoms, but preferably 0.4 to 2.0. Is in the range. When the amount of terminal vinyl is small, the amount of the terminal unsaturated polypropylene introduced into the main chain in the subsequent step (B) is low, and the amount of grafted olefin polymer produced is small, so that the desired effect may not be obtained. ..

The amount of unsaturated terminals and the ratio of each terminal structure can be calculated by ¹ H-NMR measurement, as described above, for example, according to the method described in Macromolecular Rapid Communications 2000, 1103.

[Step (B)]
In the step (B), the terminal unsaturated polypropylene produced in the step (A), ethylene, and a carbon atom are produced in the presence of an olefin polymerization catalyst containing the bridged metallocene compound [B] represented by the above formula [B]. It is a step of copolymerizing with at least one α-olefin selected from α-olefins of several 3 to 20.

In the step (B), it is important to select a catalyst that exhibits sufficient activity at high temperatures, has high copolymerizability, and is capable of having a high molecular weight. The terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and has a sterically bulky structure, so that it is difficult to polymerize as compared with a linear vinyl monomer. Further, the terminal vinyl polypropylene is less likely to be copolymerized under a low temperature condition where a polymer is precipitated. For this reason, the catalyst is preferably required to exhibit sufficient activity at a polymerization temperature of 90° C. or higher and to have a main chain with a desired molecular weight.

From such a viewpoint, in order to obtain the olefin resin (β) containing a high content of polypropylene according to the present invention, the crosslinked metallocene compound [B] is preferably used in the step (B).

The bridged metallocene compound [B] is at least one selected from terminal unsaturated polypropylene produced in the step (A) in combination with the compound [C] described below, ethylene, and an α-olefin having 3 to 20 carbon atoms. It functions as a catalyst for olefin polymerization that copolymerizes with α-olefin.

Hereinafter, the features of the chemical structure of the bridged metallocene compound [B] used in the present invention will be described.
The bridged metallocene compound [B] has the following features [m1] and [m2] structurally.

[M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other one is a fluorenyl group having a substituent (hereinafter also referred to as "substituted fluorenyl group"). I say.).

[M2] The two ligands are bound to each other by an aryl group-containing covalent bond bridging part (hereinafter also referred to as "bridging part") composed of a carbon atom or a silicon atom having an aryl group.
Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the cross-linking portion and other characteristics of the bridged metallocene compound [B] will be sequentially described.

(Cyclopentadienyl group which may have a substituent)
In the formula [B], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than the silicon-containing group, As a structure in which pyrene is favorably incorporated, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or at ^{least one} of R ¹ , R ² , R ³ and R ⁴ is a methyl group. Structures are particularly preferred.

(Substituted fluorenyl group)
In the formula [B], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than the silicon-containing group, and a hydrogen atom or a hydrocarbon group. Alternatively, silicon-containing groups are preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and a hydrogen atom, a hydrocarbon group and a silicon-containing group are R ⁷ and R ¹⁰ are preferably the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group and a silicon-containing group. A group is preferred; R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that “R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the perspective of polymerization activity, it is preferred that R ⁶ and R ¹¹ are not both a hydrogen atom; still more preferably R ^6, R ^7, R ¹⁰ and R ¹¹ are not both a hydrogen atom; R ⁶ and R ¹¹ Is particularly preferably the same group selected from a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ are particularly preferably the same group selected from a hydrocarbon group and a silicon-containing group. It is also preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic ring or aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic ring or aromatic ring.

Examples and preferred groups of the hydrocarbon group for R ^{5 to} R ¹² include, for example, a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms, hereinafter referred to as “hydrocarbon group (f1)”). Or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms, hereinafter sometimes referred to as “silicon-containing group (f2)”). In addition, examples of the substituent in the substituted cyclopentadienyl group include a hetero atom-containing group (excluding the silicon-containing group (f2)) such as a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. As the hydrocarbon group (f1), specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, Linear hydrocarbon group such as n-nonyl group, n-decanyl group and allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthyl group Group, biphenyl group, phenanthryl group, anthracenyl group and other cyclic unsaturated hydrocarbon groups and their nuclear alkyl substitution products; at least one hydrogen atom of a saturated hydrocarbon group such as benzyl group and cumyl group is substituted with an aryl group And the groups mentioned above. The silicon-containing group (f2) in R ^{5 to} R ¹² is preferably a silicon-containing group having 1 to 20 carbon atoms, and for example, a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group. Examples thereof include an alkylsilyl group (eg: trimethylsilyl group) and an arylsilyl group (eg: triphenylsilyl group).

Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) are methoxy group, ethoxy group, phenoxy group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group. , Pentafluorophenyl group.

Among the hydrocarbon groups (f1), a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n- Preferred examples include a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group.

As the substituted fluorenyl group in the case where R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic ring or aromatic ring, compounds represented by general formulas [II] to [VI] described later can be used. The group derived from is mentioned as a suitable example.

(Cross section)
In formula [B], R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. An important point in the method for producing an olefin polymer is that the bridging atom Y ¹ of the bridging portion has aryl groups R ¹³ and R ^14, which may be the same or different from each other. For ease of production, it is preferable that R ¹³ and R ¹⁴ are the same as each other.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of aromatic hydrogen (sp ² type hydrogen) of these groups is substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2), a halogen atom and a halogenated hydrocarbon group.

Specific examples of the aryl group include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms such as phenyl group, naphthyl group, anthracenyl group and biphenyl group; tolyl group, isopropylphenyl group, n-butylphenyl. Group, aryl group substituted with an alkyl group such as t-butylphenyl group, dimethylphenyl group; aryl group substituted with a cycloalkyl group such as cyclohexylphenyl group; halogenated aryl group such as chlorophenyl group, bromophenyl group, dichlorophenyl group, dibromophenyl group A halogenated alkyl group-substituted aryl group such as a (trifluoromethyl)phenyl group and a bis(trifluoromethyl)phenyl group. The position of the substituent is preferably the meta position and/or the para position. Among these, a substituted phenyl group having a substituent at the meta position and/or the para position is more preferable.

(Other characteristics of cross-linked metallocene compound)
In the formula [B], Q can be coordinated with a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anion ligand or a lone pair of electrons. It represents a neutral ligand, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

Examples of the hydrocarbon group for Q include a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -A trimethylbutyl group and a neopentyl group are mentioned. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

Examples of the halogenated hydrocarbon group for Q include groups in which at least one hydrogen atom of the above hydrocarbon group for Q is substituted with a halogen atom.
In the formula [B], M ¹ represents a zirconium atom or a hafnium atom, and the hafnium atom is preferable because it can copolymerize the terminal unsaturated polypropylene with high efficiency and can control the molecular weight to be high. It is important to copolymerize the terminally unsaturated polypropylene with high efficiency and to use a catalyst having the ability to control the molecular weight to ensure high productivity. This is because it is desirable to carry out the reaction under high temperature conditions in order to secure high productivity, but under the high temperature conditions, the molecular weight produced tends to decrease.

(Exemplary preferred cross-linked metallocene compound [B])
Specific examples of the bridged metallocene compound [B] are shown below in formulas [II] to [VI]. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [II], and octamethyltetrahydrodicyclopentafluorenyl is represented by a formula [III]. Is a group derived from a compound having a structure represented by the formula, and dibenzofluorenyl is a group derived from a compound having a structure represented by the formula [IV]: 1,1′,3,6,8,8′-hexamethyl- 2,7-Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [V], and is 1,3,3',6,6',8-hexamethyl-2,7- Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VI].

As the bridged metallocene compound [B], for example,
Diphenylmethylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl)hafnium dichloride, diphenylmethylene (cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylmethylene (Cyclopentadienyl)(1,3,3′,6,6′,8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(2,7 -Diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3 ,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(p-tolyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(1,3,3',6 ,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,3,6,7-tetramethylfluorenyl)hafnium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(1,3,3',6 ,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium Dichloride,
Di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(1,3,3',6 ,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium Dichloride,
Di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(3,6-di tert-Butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadiene) (Enyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(1 ,3,3',6,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl -3,6-Ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium Dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene( Cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,3,6 ,7-Tetra-tert-butylfluorenyl)hafnium dichloride,
Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl) (3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(m- Trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl) Hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium Dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride , Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl) Methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7 -(Trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3, 6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl) (3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p- Trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl) Hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium Dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride , Di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl) Methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7 -(Trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3, 6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl) (3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p- tert-Butyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl) Hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium Dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride , Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl) Methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7 -(Trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3, 6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl) (3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p- n-Butyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl) Hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium Dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride , Di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl) Methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7 -(Trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3, 6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,
Di(p-biphenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(1,3,3',6 ,6′,8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium Dichloride,
Di(1-naphthyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(1,3,3',6 ,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium Dichloride,
Di(2-naphthyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(3,6-ditert- Butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyl Tetrahydrodicyclopentafluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(1,1 ',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(1,3,3',6 ,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert- Butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-( Dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium Dichloride,
Di(m-tolyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorene Nyl)hafnium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride,
Di(p-isopropylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl ) Hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(3 ,6-ditert-butylfluorenyl)hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (Cyclopentadienyl) (1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (Cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3 ,6-ditert-butylfluorenyl)hafnium dichloride and diphenylsilylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride.

As the bridged metallocene compound [B], a compound in which "dichloride" of the above-exemplified compound is replaced by "difluoride", "dibromide", "diaiodide", "dimethyl" or "methylethyl", "cyclopentadienyl" To "3-tert-butyl-5-methyl-cyclopentadienyl", "3,5-dimethyl-cyclopentadienyl", "3-tert-butyl-cyclopentadienyl" or "3-methyl-cyclo Compounds replaced with "pentadienyl" and the like can also be mentioned.

The above bridged metallocene compound can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in International Publication No. 01/27124 pamphlet and International Publication No. 04/029062 pamphlet by the present applicant.

The bridged metallocene compound [B] as described above may be used alone or in combination of two or more kinds.
The step (B) can be carried out in solution (dissolution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin-based polymer is used, but there is a step of obtaining the following polymerization reaction solution. Is preferred.

The step of obtaining a polymerization reaction solution means that a crosslinked metallocene compound [B], preferably R ¹³ and R ¹⁴ bonded to Y ¹ in the above general formula [B], is obtained by using an aliphatic hydrocarbon as a polymerization solvent. Phenyl group, or a phenyl group substituted by an alkyl group or a halogen group, wherein R ⁷ and R ¹⁰ are ethylene and 3 to 3 carbon atoms in the presence of a metallocene catalyst containing a transition metal compound having an alkyl substituent. 20 is a step of obtaining a polymerization reaction liquid of a copolymer of 20 α-olefin and the terminally unsaturated polypropylene produced in the step (A).

In step (B), the terminally unsaturated polypropylene produced in step (A) is fed in solution or slurry form to the reactor in step (B). The feeding method is not particularly limited, and even if the polymerization liquid obtained in the step (A) is continuously fed to the reactor in the step (B), the polymerization liquid in the step (A) is temporarily buffered. It may be fed to the step (B) after being stored in the tank.

Examples of the polymerization solvent in the step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, xylene. And aromatic hydrocarbons such as ethylene chloride, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used alone or in combination of two or more. Further, the polymerization solvent in step (B) may be the same as or different from the polymerization solvent in step (A). Of these, aliphatic hydrocarbons such as hexane and heptane are preferable from the industrial viewpoint, and hexane is more preferable from the viewpoint of separation from the olefin resin (β) and purification.

The polymerization temperature in step (B) is preferably in the range of 90°C to 200°C, more preferably 100°C to 200°C. Such a temperature is preferable because the temperature at which the unsaturated terminal polypropylene dissolves well in the aliphatic hydrocarbon such as hexane and heptane industrially preferably used as the above-mentioned polymerization solvent is 90° C. or higher. is there. A higher temperature is preferable in order to improve the amount of polypropylene side chains introduced. Further, the temperature is preferably higher from the viewpoint of improving productivity.

The polymerization pressure in the step (B) is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction is performed in any of batch-wise, semi-continuous and continuous methods. It can be carried out. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. In the present invention, of these, it is preferable to employ the method of continuously supplying the monomer to the reactor to carry out the copolymerization.

The reaction time of the step (B) (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

In the step (B), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoint of the viscosity limit in the polymerization ability, the load of the post-treatment step (desolvent) and the productivity, it is preferably 15 to 35 wt %.

The molecular weight of the obtained copolymer can also be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Furthermore, it can be adjusted by the amount of the compound [C1] described below. Specific examples of the compound [C1] include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, its amount is appropriately about 0.001 to 100 NL per 1 kg of olefin.

[Compound [C]]
In the method for producing the olefin resin (β) according to the present invention, the transition metal compound [A] and the crosslinked metallocene compound [B] used as the olefin polymerization catalyst in the above steps (A) and (B) will be described later. It is preferable to use the compound [C].

The compound [C] reacts with the transition metal compound [A] and the bridged metallocene compound [B] to function as a catalyst for olefin polymerization. Specifically, the compound [C1] is an organometallic compound, [C2]. It is selected from an organoaluminum oxy compound and a compound which reacts with the [C3] transition metal compound [A] or the bridged metallocene compound [B] to form an ion pair. Hereinafter, the compounds [C1] to [C3] will be sequentially described.

([C1] Organometallic compound)
As the [C1] organometallic compound used in the present invention, specifically, an organoaluminum compound represented by the following general formula (C1-a), a Group 1 metal of the periodic table represented by the general formula (C1-b), and Examples thereof include complex alkylated products with aluminum, and dialkyl compounds of metals of Group 2 or Group 12 of the periodic table represented by the general formula (C1-c). The [C1] organometallic compound does not include the [C2] organoaluminumoxy compound described later.

上記一般式（Ｃ１−ａ）中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｒは０≦ｒ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｒ＋ｓ＝３である。）

In the general formula (C1-a), R ^a and R ^{b, which} may be the same or different, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen atom. Where p is 0<p≦3, q is 0≦q<3, r is 0≦r<3, s is a number 0≦s<3, and p+q+r+s=3. )

上記一般式（Ｃ１−ｂ）中、Ｍ³はＬｉ、ＮａまたはＫを示し、Ｒ^cは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示す。）

In the above general formula (C1-b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )

上記一般式（Ｃ１−ｃ）中、Ｒ^dおよびＲ^eは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｍ⁴はＭｇ、ＺｎまたはＣｄである。

In the general formula (C1-c), R ^d and R ^{e, which} may be the same or different, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg. , Zn or Cd.

Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、ｐは好ましくは１．５≦ｐ≦３の数である。）で表される有機アルミニウム化合物、

(In the formula, R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably 1.5≦p≦ An organoaluminum compound represented by the number 3),

（式中、Ｒ^aは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロン原子を示し、ｐは好ましくは０＜ｐ＜３の数である。）で表される有機アルミニウム化合物、

(In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halon atom, and p is preferably 0<p<3.). An organoaluminum compound represented,

（式中、Ｒ^aは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、ｐは好ましくは２≦ｐ＜３の数である。）で表される有機アルミニウム化合物、

(In the formula, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2≦p<3.),

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｓ＝３である。）で表される有機アルミニウム化合物。

(In the formula, R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p represents 0. <p≦3, q is 0≦q<3, s is a number 0≦s<3, and p+q+s=3).

More specific examples of the organoaluminum compound belonging to the general formula (C1-a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as;
Triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tri 2-methyl butyl aluminum, tri 3-methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4 -Tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritolylaluminum;
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 , wherein R ^a and R ^b may be the same or different from each other and have carbon atoms. 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6- Dialkyl aluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide;
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide;
Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride;
Other partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride;
Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide and the like can be mentioned.

A compound similar to (C1-a) can also be used in the present invention, and as such a compound, for example, an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) _{2 and the} like.

Examples of the compound belonging to the general formula (C1-b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (C1-c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-. Examples thereof include butyl zinc, diisobutyl zinc, bis(pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

In addition, as the [C1] organometallic compound, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, Butyl magnesium bromide, butyl magnesium chloride and the like can also be used.

Further, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium is used as the [C1] organometallic compound. You can also do it.
The above [C1] organometallic compounds may be used alone or in combination of two or more.

([C2] Organoaluminum Oxy Compound)
The [C2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Good. Specific examples of the [C2] organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the adsorbed water or crystal water with the organoaluminum compound.

(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

The aluminoxane may contain a small amount of organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be distilled off from the recovered solution of the aluminoxane, and the obtained aluminoxane may be redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above organoaluminum compounds may be used alone or in combination of two or more.

As the solvent used for the preparation of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine Hydrocarbon solvents such as halides and bromides are mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60° C. of usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom. That is, it is preferably insoluble or sparingly soluble in benzene.

Examples of the [C2] organoaluminum oxy compound used in the present invention also include boron-containing organoaluminum oxy compounds represented by the following general formula (III).

（一般式（ＩＩＩ）中、Ｒ¹⁷は炭素原子数が１〜１０の炭化水素基を示し、４つのＲ¹⁸は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。）

(In the general formula (III), R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ¹⁸ may be the same or different from each other, and have a hydrogen atom, a halogen atom and a carbon atom number. The hydrocarbon groups 1 to 10 are shown.)

The organoaluminum oxy compound containing boron represented by the general formula (III) is obtained by combining an alkylboronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert gas atmosphere under an inert solvent. It can be produced by reacting at -80°C to room temperature for 1 minute to 24 hours.

（一般式（ＩＶ）中、Ｒ¹⁹は前記一般式（ＩＩＩ）におけるＲ¹⁷と同じ基を示す。）

(In the general formula (IV), R ¹⁹ represents the same group as R ¹⁷ in the general formula (III).)

Specific examples of the alkylboronic acid represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid and n-hexylboron. Acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorofernylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like can be mentioned. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
The above [C2] organoaluminum oxy compounds may be used alone or in combination of two or more.

(Compound that reacts with [C3] transition metal compound [A] or bridged metallocene compound [B] to form an ion pair)
As the compound [C3] (hereinafter, referred to as “ionized ionic compound”) which is used in the present invention and which reacts with the transition metal compound [A] or the bridged metallocene compound [B] to form an ion pair, JP-A-1 is used. No. 501501, JP 1-502036, JP 3179005, JP 3179006, JP 3-207703, JP 3-207704, USP-5321106, etc. Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group, or fluorine) Examples thereof include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, Examples include tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.
Examples of the ionic compound include compounds represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ²⁰はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ²¹〜Ｒ²⁴は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In the general formula (V), R ²⁰ is H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation having a transition metal, and R ^{21 to} R ²⁴ Are the same or different from each other and are an organic group, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cations include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dimethylanilinium cation; N,N-diethylanilinium cation, N,N-dialkylanilinium cation such as N,N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di(isopropyl)ammonium cation, dicyclohexylammonium cation And so on.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

R ¹⁵ is preferably a carbonium cation or an ammonium cation, particularly preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation or an N,N-diethylanilinium cation.

Examples of the ionic compound also include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl). ) Boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra (M,m-Dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, tri( Examples thereof include n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N,2,4, and Examples thereof include 6-pentamethylanilinium tetra(phenyl)boron.

Specific examples of the dialkyl ammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

Further, as ionic compounds, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenyl Examples also include a cyclopentadienyl complex, an N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VI) or (VII).

（式（ＶＩ）中、Ｅｔはエチル基を示す。）

(In the formula (VI), Et represents an ethyl group.)

（式（ＶＩＩ）中、Ｅｔはエチル基を示す。）

(In the formula (VII), Et represents an ethyl group.)

Specific examples of the borane compound that is an example of the ionized ionic compound (compound [C3]) include, for example, decaborane;
Bis[tri(n-butyl)ammonium]nonaborate, Bis[tri(n-butyl)ammonium]decaborate, Bis[tri(n-butyl)ammonium]undecaborate, Bis[tri(n-butyl)ammonium]dodecaborate Anions salts such as bis[tri(n-butyl)ammonium]decachlorodecaborate and bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
Of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridododecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydridododecaborate)nickelate (III) Examples include salt.

Specific examples of the carborane compound, which is an example of the ionized ionic compound, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, and dodecahydride-1-phenyl-1,3-. Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 ,7-Dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, Dodecahydride-11-Methyl-2,7-dicarbaundodecaborane, Tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carumbadecaborate, tri(n-butyl)ammonium 7 -Carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8- Methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl- 7,9-Dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7, Salts of anions such as 8-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7) ,8-Dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate (III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate (III), tri(n-butyl)ammonium bis( Tribromooctahydride-7,8-dicarbaundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate (III) , Bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-cal Examples thereof include salts of metal carborane anions such as boundecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV). To be

The heteropoly compound, which is an example of the ionized ionic compound, contains an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. It is a compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorous Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdo niobate, and salts of these acids, but are not limited thereto. In addition, as the salt, for example, a metal of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium or the like of the above-mentioned acid. Examples thereof include salts and organic salts such as triphenylethyl salt.

An isopoly compound, which is an example of an ionized ionic compound, is a compound composed of a metal ion of one atom selected from vanadium, niobium, molybdenum, and tungsten, and should be regarded as a molecular ionic species of a metal oxide. You can Specific examples thereof include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. As the salt, for example, a salt of the above-mentioned acid with a metal of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium or the like. , And organic salts such as triphenylethyl salt.

The above-mentioned ionized ionic compounds (compounds that react with the [C3] transition metal compound [A] and the bridged metallocene compound [B] to form an ion pair) may be used alone or in combination of two or more. ..

When a [C2] organoaluminumoxy compound such as methylaluminoxane as a cocatalyst component is used in combination with the transition metal compound [A] and the bridged metallocene compound [B], a very high polymerization activity for an olefin compound is exhibited.

The above [C3] ionized ionic compounds may be used alone or in combination of two or more.
The organometallic compound [C1] has a molar ratio (C1/M) of the organometallic compound [C1] and the transition metal atom (M) in the transition metal compound [A] in the step (A) to the step (B). In (), the molar ratio (C1/M) to the transition metal atom (M) in the bridged metallocene compound [B] is usually 0.01 to 100,000, preferably 0.05 to 50,000. ..

The organoaluminum oxy compound [C2] is a molar ratio (C2/M) between the aluminum atom in the organoaluminum oxy compound [C2] and the transition metal atom (M) in the transition metal compound [A] in the step (A). ), in the step (B), the molar ratio (C2/M) to the transition metal atom (M) in the bridged metallocene compound [B] is usually 10 to 500,000, preferably 20 to 100,000. Used.

The ionized ionic compound [C3] has a molar ratio (C3/M) of the ionized ionic compound [C3] and the transition metal atom (M) in the transition metal compound [A] in the step (A) to the step In (B), the amount is such that the molar ratio (C2/M) to the transition metal atom (M) (hafnium atom) in the crosslinked hafnocene compound [B] is usually 1 to 10, preferably 1 to 5. Used.

[Step (C)]
The method for producing the olefin resin (β) may include, in addition to the steps (A) and (B), if necessary, a step (C) of recovering the polymer produced in the step (B). This step is a step of separating the organic solvent used in steps (A) and (B), extracting the polymer and converting it into a product form, and producing an existing polyolefin resin such as solvent concentration, extrusion degassing, pelletizing and the like. There is no particular limitation as long as it is a process.

<Olefin resin (γ)>
The propylene resin composition of the invention is characterized by containing an olefin resin (γ) as an essential component in addition to the propylene resin (α) and the olefin resin (β) described above. The olefin-based resin (γ) according to the present invention may be composed of only one kind of olefin-based polymer or may be composed of two or more kinds of olefin-based polymers. It is characterized by satisfying all of γ-I) to (γ-III).
(Γ-I) The olefin resin (γ) is an ethylene/α-olefin copolymer.
(Γ-II) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30°C.
(Γ-III) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl/ or less, and these requirements (γ-I) to (γ-III) will be specifically described.

[Requirements (γ-I)]
The olefin-based resin (γ) is an ethylene/α-olefin copolymer, preferably from a repeating unit derived from ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. It is composed of repeating units that are guided. Specific examples of the α-olefin having 3 to 20 carbon atoms which is copolymerized with ethylene in the ethylene/α-olefin copolymer include propylene, 1-butene, 2-methyl-1-propene and 2- Methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1- Pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl -1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1- Pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like can be mentioned.

More preferred are α-olefins having 3 to 10 carbon atoms, and even more preferred are α-olefins having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Examples thereof include branched olefins such as 3-methyl-1-butene, and among them, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, 1-butene, 1-pentene and 1-hexene. , 1-octene is more preferred. By using 1-butene, 1-pentene, 1-hexene, or 1-octene as the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene, a propylene-based resin composition having the best physical property balance can be obtained. To be

The proportion of repeating units derived from ethylene is in the range of 50 to 90 mol%, preferably 60 to 90 mol%, more preferably 70 to 90 mol%, and even more preferably 75 to 85 mol% based on all repeating units. The proportion of repeating units derived from α-olefin is in the range of 10 to 50 mol%, preferably 10 to 40 mol%, more preferably 10 to 30 mol%, and even more preferably 15 to 25 mol% based on all repeating units. ..

Depending on the type of α-olefin used, the relationship between the ratio of repeating units derived from ethylene and α-olefin and the glass transition temperature (Tg) is different, but the range of the glass transition temperature (Tg) described in the requirement (γ-II). In order to achieve the above, the ratio of repeating units of ethylene and α-olefin is preferably within the above range.

When the proportion of repeating units derived from ethylene and α-olefin in the main chain is in the above range, the olefin resin (γ) has excellent flexibility, and the propylene resin composition containing the olefin resin (γ) The product has excellent impact resistance.

[Requirements (γ-II)]
The glass transition temperature (Tg) of the olefin resin (γ) is in the range of −80 to −30° C., preferably −80 to −40° C., and more preferably −70° C. to −50° C.
With respect to the glass transition temperature (Tg), the propylene resin composition containing the olefin resin (β) exhibits good impact resistance because the glass transition temperature (Tg) is within the above range. The glass transition temperature (Tg) within the above range can be obtained by controlling the type and composition of the α-olefin of the ethylene/α-olefin copolymer as described above.

[Requirements (γ-III)]
The olefin resin (γ) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.5 to 5.0 dl/g. The intrinsic viscosity [η] is preferably 1.0 to 4.0 dl/g, more preferably 1.0 to 3.0 dl/g. When the intrinsic viscosity [η] is in the above range, the propylene-based resin composition containing the olefin resin (γ) has good rigidity and mechanical strength in addition to impact resistance, and further has excellent molding properties. It also has workability.

The MFR of the olefin resin (γ) is not particularly limited, but it is preferable from the viewpoint of impact resistance that the MFR of the olefin resin (γ) is 0.01 to 0.3 g/10 minutes.
A commercially available elastomer may be used as the olefin resin satisfying the above requirements, and specific examples of the commercially available elastomer include Tuffmer A (manufactured by Mitsui Chemicals, Inc.) and Engage (Dow Chemical). What was manufactured by the method may be used.

<Method for producing olefin resin (γ)>
The olefin resin (γ) is produced, for example, by a production method including the following step (γ-A).
(Γ-A) Ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table. The step of copolymerizing.

The transition metal compound of Group 4 of the periodic table, in combination with the compound [C] described in the above step [B], is ethylene and at least one α selected from α-olefins having 3 to 20 carbon atoms. -It functions as an olefin polymerization catalyst that copolymerizes with an olefin, and is not particularly limited, but a catalyst that exhibits a high olefin polymerization activity and produces a high molecular weight polymer is preferable.

The transition metal compound of Group 4 of the periodic table is a superordinate concept of the bridged metallocene compound [B], and the bridged metallocene compound [B] may be actually used in this step.
The propylene resin composition of the present invention is characterized by containing a propylene resin (α), an olefin resin (β) and an olefin resin (γ) as essential components.

There is no particular limitation on the content ratio of the propylene-based resin (α), the olefin-based resin (β), and the olefin-based resin (γ), while maintaining good physical properties such as the rigidity and hardness of the propylene-based resin, The content ratio of improving the impact resistance of the propylene-based resin (α) is preferably 50 to 90 parts by weight, more preferably 60 to 90 parts by weight, and further preferably 70 to 80 parts by weight. The total content of the olefin resin (β) and the olefin resin (γ) is preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, and further preferably 20 to 30 parts by weight. However, the total content of the propylene resin (α), the olefin resin (β) and the olefin resin (γ) is 100 parts by weight.

Further, the content ratio of the olefin resin (β) and the olefin resin (γ) is not particularly limited, but the weight ratio of the olefin resin (β) and the olefin resin (γ) ((β)/(γ )) is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and further preferably 85/15 to 15/85.

Since the content ratios of the propylene resin (α), the olefin resin (β) and the olefin resin (γ) are within the above range, the propylene resin composition of the present invention has a rigidity and hardness which are inherent to the propylene resin. The impact resistance and toughness are improved while maintaining good physical properties, and it can be suitably used for the production of various molded products.

The propylene-based resin composition according to the present invention can be blended with other resins, rubbers, inorganic fillers, organic fillers, etc. within a range that does not impair the object of the present invention, and also has a weather resistance stabilizer and heat resistance stability. Additives such as agents, antistatic agents, antislip agents, antiblocking agents, antifog agents, lubricants, pigments, dyes, plasticizers, antiaging agents, hydrochloric acid absorbents, antioxidants, and crystal nucleating agents. be able to. In the propylene-based resin composition according to the present invention, the addition amount of the other resin, the other rubber, the inorganic filler, the additive, etc. is not particularly limited as long as it does not impair the object of the present invention. Absent.

The method for preparing the propylene-based resin composition in the present invention is not particularly limited, such as a melting method and a solution method, but a melt-kneading method is preferable in practical use. As the melt-kneading method, the melt-kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are uniformly mixed by a Henschel mixer, a ribbon blender, a V-type blender or the like together with the above-mentioned additives which are additional components, if necessary, and then uniaxial or multiaxial kneading extrusion. It can be prepared by kneading with a machine, a kneading roll, a batch kneader, a kneader, a Banbury mixer, or the like.

The melt-kneading temperature of each component (for example, cylinder temperature in the case of an extruder) is usually 170 to 250°C, preferably 180 to 230°C. Furthermore, the kneading order and method of each component are not particularly limited.

<Molded body>
The propylene-based resin composition can improve impact resistance while maintaining the rigidity of the propylene-based resin, and has an excellent balance between rigidity and impact resistance. Various moldings of the propylene-based resin composition by known molding methods such as injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calender molding, and foam molding. Can be molded into. The molded product obtained from the propylene-based resin composition can be applied to various known applications such as automobile parts, containers for food applications and medical applications, packaging materials for food applications and electronic materials.

The molded article made of the propylene-based resin composition has excellent balance between rigidity and impact resistance, high surface hardness, and excellent chemical resistance, and therefore can be used for various automobile parts. For example, automotive exterior parts such as bumpers, side moldings, aerodynamic undercovers, vehicle interior parts such as instrument panels and interior trims, outer panel parts such as fenders, door panels, steps, engine covers such as engine covers, fans and fan shrouds. It can be used for parts.

As a container for food use or medical use, for example, tableware, retort container, frozen storage container, retort pouch, microwave oven heat-resistant container, frozen food container, frozen dessert cup, cup, beverage bottle and other food containers, retort container, bottle. Containers, etc., blood transfusion set, medical bottle, medical container, medical hollow bottle, medical bag, infusion bag, blood storage bag, infusion bottle chemical container, detergent container, cosmetic container, perfume container, toner container, etc. ..

As the packaging material, for example, food packaging material, meat packaging material, processed fish packaging material, vegetable packaging material, fruit packaging material, fermented food packaging material, confectionery packaging material, oxygen absorbent packaging material, retort food packaging material, freshness Holding film, pharmaceutical packaging, cell culture bag, cell inspection film, bulb packaging, seed packaging, vegetable/mushroom cultivation film, heat-resistant vacuum forming container, side dish container, side dish lid, commercial wrap film, home use Wrap films, baking cartons, and the like.

Examples of films, sheets, and tapes include protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electrical parts and appliances, protective films for mobile phones, and personal computers. Protective film, masking film, capacitor film, reflective film, laminate (including glass), radiation resistant film, gamma ray resistant film, protective film such as porous film,
Other applications include, for example, housings for home appliances, hoses, tubes, wire coatings, insulators for high-voltage wires, cosmetics/perfume spray tubes, medical tubes, infusion tubes, pipes, wire harnesses, motorcycles, and railways. Interior materials for vehicles, aircraft, ships, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnish, console box, armrests, airbag case lids, shift knobs, assist grips, side steps Mats, reclining covers, seats in trunks, seat belt buckles, inner/outer moldings, roof moldings, molding materials such as belt moldings, automotive seal materials such as door seals and body seals, glass run channels, mudguards, kicking plates, steps Mats, license plate housings, automotive hose members, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions, and other automotive interior and exterior materials, damping tires, static tires, cars Special tires such as race tires, radio-controlled tires, packings, automobile dust covers, lamp seals, automotive boot materials, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, furniture, footwear, clothing and bags.・Surface materials such as building materials, building sealing materials, waterproof sheets, building material sheets, building material gaskets, building material window films, iron core protection members, gaskets, doors, door frames, window frames, margins, skirting boards, opening frames, etc. , Floor materials, ceiling materials, wallpaper, health products (eg non-slip mats/sheets, anti-tipping films/mats/sheets), health equipment parts, shock absorbing pads, protectors/protectors (eg helmets, guards), Sports equipment (eg, sports grips, protectors), sports equipment, rackets, mouth guards, balls, golf balls, transportation equipment (eg: shock absorbing grips for transport, shock absorbing sheets), vibration control pallets, shock absorbing dampers, Insulators, shock absorbing materials for footwear, shock absorbing foam, shock absorbing films and other shock absorbing materials, grip materials, sundries, toys, shoe soles, soles, shoe midsole/inner soles, soles, sandals, suckers, Toothbrush, flooring material, gymnastics mat, electric tool member, agricultural equipment member, heat dissipation material, transparent substrate, soundproofing material, ku Application materials, electric cables, shape memory materials, medical gaskets, medical caps, drug stoppers, gaskets, baby foods, dairy products, pharmaceuticals, sterile water, etc. Packing materials for various uses, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, audio protection Precision equipment such as vibration materials, OA equipment support members, heat resistant packing for OA, animal cages, beakers, physics and chemistry equipment such as measuring cylinders, optical measurement cells, costume cases, clear cases, clear files, clear sheets, desk mats, Examples of applications as fibers include non-woven fabrics, elastic non-woven fabrics, fibers, waterproof fabrics, breathable fabrics and cloths, diapers, sanitary products, hygiene products, filters, bag filters, dust collecting filters, air cleaners, hollow fiber filters. , A water filter, a gas separation membrane, and the like.

Among them, the molded product obtained from the propylene-based resin composition can improve impact resistance while maintaining rigidity, and is excellent in the balance between rigidity and impact resistance, so that it is particularly useful for bumpers and instrument panels. It can be suitably used for automobile interior/exterior materials, outer plate materials, food containers, and beverage containers.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
In the following examples, the physical properties of the propylene resin (α), the olefin resin (β), the olefin resin (γ) and the propylene resin composition were measured by the following methods.

(Method for measuring physical properties of propylene resin (α))
(1) Melt flow rate (MFR: [g/10 minutes])
The melt flow rate was measured with a 2.16 kg load according to ASTM D1238E. The measurement temperature was 230°C.
(2) Isotactic pentad fraction (mmmm: [%])
The pentad fraction (mmmm, %), which is one of the indicators of the stereoregularity of the polymer and whose microtacticity was investigated, was assigned based on Macromolecules 8,687 (1975) in the propylene-based resin (α). It was calculated from the peak intensity ratio of the 13 C-NMR spectrum. The 13C-NMR spectrum was measured by using an apparatus of EX-400 manufactured by JEOL, using TMS as a reference, a temperature of 130° C., and an o-dichlorobenzene solvent.

(Method for measuring physical properties of olefin resin (β), olefin resin (γ) and terminal unsaturated polypropylene)
(3) Measurement of melting point (Tm) and heat of fusion ΔH The measurement of melting point (Tm) and heat of fusion ΔH was performed by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter [RDC220 manufactured by SII], about 10 mg of a sample was heated from 30° C. to 200° C. at a heating rate of 50° C./min in a nitrogen atmosphere, and was held at that temperature for 10 minutes. Further, the temperature was decreased to 30° C. at a temperature decreasing rate of 10° C./minute, and the temperature was maintained for 5 minutes, and then the temperature was increased to 200° C. at a temperature increasing rate of 10° C./minute. The endothermic peak observed during this second temperature rise was taken as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm). The heat of fusion ΔH was calculated by calculating the area of the melting solution peak. When the melting peaks were multimodal, the total melting peak area was calculated.

(4) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) was measured by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter [RDC220 manufactured by SII], about 10 mg of a sample was heated from 30° C. to 200° C. at a heating rate of 50° C./min in a nitrogen atmosphere, and was held at that temperature for 10 minutes. Further, the temperature was decreased to −100° C. at a temperature decreasing rate of 10° C./minute, and the temperature was maintained for 5 minutes, and then the temperature was increased to 200° C. at a temperature increasing rate of 10° C./minute. The glass transition temperature (Tg) is sensed as the DSC curve bends due to a change in the specific heat and the base line moves in parallel during the second temperature rise. The glass transition temperature (Tg) was defined as the temperature at the intersection of the tangent line of the baseline at a temperature lower than this bending and the tangent line of the maximum inclination in the bent portion.

(5) Measurement of Ratio P of Propylene Polymer Contained in Olefin Resin to Olefin Resin (β) As described above, the weight of the terminal unsaturated polypropylene used in the step (B) and the obtained olefin resin (β ) And the ratio with the weight.

(6) Cross-fractionation chromatograph (CFC) measurement The ratio E of the component whose peak value of the differential elution curve measured by cross-fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent is less than 65° C. to the olefin resin and The method for calculating the proportion (wt%) of the orthodichlorobenzene-soluble component at 50° C. or lower is described in the section of requirement (III) and requirement (XI), but specifically in Examples and Comparative Examples, It is as follows.
Apparatus: Cross fractionation chromatograph CFC2 (Polymer ChAR), Detector (built-in): Infrared spectrophotometer IR ⁴ (Polymer ChAR), Detection wavelength: 3.42 μm (2,920 cm-1); Fixed, sample concentration: 120 mg /30 mL, injection amount: 0.5 mL, temperature lowering time: 1.0° C./min, elution category: 4.0° C. interval (−20° C. to 140° C.), GPC column: Shodex HT-806M×3 (Showa Denko) , GPC column temperature: 140° C., GPC column calibration: monodisperse polystyrene (Tosoh Corporation), molecular weight calibration method: general-purpose calibration method (polystyrene conversion), mobile phase: o-dichlorobenzene (BHT addition), flow rate: 1. 0 mL/min.

In the calculation of the ratio E of the component having a peak temperature of less than 65°C to the olefin resin, the differential elution curve obtained by the CFC measurement is peak-separated by the normal distribution curve, and the ratio of the elution component having the peak temperature of 65°C or higher ( wt%), the sum E _(>65 ° C. ₎ was determined, and E=100−E _(>65 ° C. ₎ .
The ratio (wt%) of the ortho-dichlorobenzene-soluble component at 50°C or less is the cumulative elution amount (including the -20°C-soluble component) at 50°C of the cumulative elution curve by the CFC measurement.

(7) Measurement of intrinsic viscosity The intrinsic viscosity [η] was measured in decalin at 135°C.
Specifically, after dissolving about 20 mg of resin in 25 ml of decalin, the specific viscosity ηsp was measured in an oil bath at 135° C. using an Ubbelohde viscometer. After adding 5 ml of decalin to the decalin solution to dilute it, the specific viscosity ηsp was measured in the same manner as above.
This dilution operation was repeated twice more, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl/g) (see the following formula 1).

(8) Melt flow rate (MFR [g/10min])
The melt flow rate was measured with a 2.16 kg load according to ASTM D1238E. The measurement temperature was 190°C.

(9) ¹³ C-NMR measurement For the purpose of analyzing the composition ratio of ethylene and α-olefin of the polymer, ¹³ C-NMR measurement was carried out under the following conditions. Apparatus: AVANCEIII500 CryoProbe Prodigy type nuclear magnetic resonance apparatus manufactured by Bruker BioSpin, measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45° (5.00 μsec), number of points: 64 k , Measurement range: 250 ppm (-55 to 195 ppm), repetition time: 5.5 seconds, integration number: 512 times, measurement solvent: orthodichlorobenzene/benzene-d ₆ (4/1 v/v), sample concentration: ca ． 60 mg/0.6 mL, measurement temperature: 120° C., window function: exponential (BF: 1.0 Hz), chemical shift standard: benzene-d ₆ (128.0 ppm).

(10) ¹ H-NMR measurement In order to analyze the terminal structure of terminally unsaturated polypropylene, ¹ H-NMR measurement was carried out under the following conditions. Apparatus: ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL, Measurement nucleus: ¹³ H (400 MHz), measurement mode: single pulse, pulse width: 45° (5.25 μsec), number of points: 32 k, measurement range: 20 ppm (- 4 to 16 ppm), repetition time: 5.5 seconds, number of integrations: 64 times, measurement solvent: 1,1,2,2-tetrachloroethane-d2, sample concentration: ca. 60 mg/0.6 mL, measurement temperature: 120° C., window function: exponential (BF: 0.12 Hz), chemical shift standard: 1,1,2,2-tetrachloroethane (5.91 ppm).

(11) GPC measurement For molecular weight analysis of the polymer, GPC analysis was performed under the following conditions. Device: Waters, Alliance GPC 2000 type, column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm x length 30 cm), column temperature: 140°C, mobile phase: orthodichlorobenzene (0) 0.025% dibutylhydroxytoluene), detector: differential refractometer, flow rate: 1.0 mL/min, sample concentration: 0.15% (w/v), injection amount: 0.5 mL, sampling time interval: 1 second , Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).
(Method for measuring physical properties of propylene resin composition)
The methods for measuring the physical properties of the propylene resin composition are shown below.

(12) Tensile test The tensile test was performed under the following conditions.
<Measurement conditions>
Test piece: JIS K7162-BA dumbbell
5mm (width) x 2mm (thickness) x 75mm (length)
Tensile speed: 500mm/min Distance between spans: 58mm
Temperature: 23 ℃

(13) Izod impact test The Izod impact test was performed under the following conditions according to ASTM D256.
<Test conditions>
Hammer capacity: 3.92J
Swing angle: 149.0°C
Notch is machined Temperature: -40℃

(14) High-speed surface impact test The high-speed surface impact test was performed using a 3 mm thick square plate with a high-speed impact tester under the following conditions.
<Test conditions>
Strike diameter: 1/2 inch φ
Support base diameter: 1 inch φ
Test speed: 5m/s
Temperature: 23 ℃

[Example 1]
(Production of propylene-based resin (α-1))
(1) Preparation of Solid Titanium Catalyst Component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130° C. for 2 hours to form a uniform solution, and then anhydrous phthalate was added to this solution. 21.3 g of acid was added, and the mixture was further stirred and mixed at 130° C. for 1 hour to dissolve phthalic anhydride.

After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was added dropwise to 200 ml of titanium tetrachloride kept at -20°C over 1 hour. After the completion of the dropwise addition, the temperature of this mixed solution was raised to 110° C. over 4 hours, and when it reached 110° C., 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours.

After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration and washed sufficiently with decane and hexane at 110° C. until no free titanium compound was detected.

Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the washing liquid of the above solid catalyst component was sampled with a syringe and put into 100 ml of a branch Schlenk previously purged with nitrogen. Next, hexane was dried in a nitrogen stream and further vacuum dried for 30 minutes. To this, 40 ml of ion-exchanged water and 10 ml of (1+1) sulfuric acid were added and stirred for 30 minutes. This aqueous solution was passed through a filter paper and transferred to a 100 ml volumetric flask, and subsequently 1 ml of concentrated H ₃ PO ₄ as a masking agent for iron (II) ions and 5 ml of 3% H ₂ O ₂ as a coloring reagent for titanium were added, and ion-exchanged water was added. The volume was raised to 100 ml. This volumetric flask was shaken and mixed, and 20 minutes later, the absorbance at 420 nm was observed using a UV meter. The free titanium was washed and removed until the absorption was no longer observed.

The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.3% by weight titanium, 61% by weight chlorine, 19% by weight magnesium, and 12.5% by weight DIBP.

(2) Production of prepolymerization catalyst 100 g of solid titanium catalyst component (A), 39.3 mL of triethylaluminum, and 100 L of heptane were put into an autoclave with a stirrer having an internal volume of 200 L, the internal temperature was kept at 15 to 20° C., and 600 g of propylene was put. The reaction was carried out for 60 minutes with stirring to obtain a catalyst slurry.

(3) Main Polymerization 43 kg/hour of propylene, 177 NL/hour of hydrogen, and 0.58 g/hour of triethylaluminum as a solid catalyst component of the catalyst slurry produced in (2) of propylene in a circulation type tubular polymerization vessel with an internal capacity of 58 L. Was continuously fed at 3.1 ml/hour and dicyclopentyldimethoxysilane at 3.3 ml/hour, and polymerization was carried out in a full liquid state in which no gas phase existed. The temperature of the tubular polymerization vessel was 70° C., and the pressure was 3.53 MPa/G.

The obtained slurry was sent to a vessel polymerization vessel with an internal volume of 100 L equipped with a stirrer for further polymerization. Propylene was supplied to the polymerization vessel at 45 kg/hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.2 mol %. Polymerization was performed at a polymerization temperature of 70° C. and a pressure of 3.28 MPa/G.

The resulting propylene homopolymer resin (α-1) was vacuum dried at 80°C. Regarding the physical properties of the propylene homopolymer resin (α-1), the melt flow rate (MFR) was 30 g/10 minutes and the isotactic pentad fraction (mmmm) was 97.8%.

(Production of olefin resin (β-1))
Step (A): Production of Terminal Unsaturated Polypropylene (M-1) Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride used as a catalyst was synthesized according to the method disclosed in Japanese Patent No. 3737134. ..

1.5 L of toluene was placed in a glass reactor having an internal volume of 2 L that had been sufficiently replaced with nitrogen, and then the temperature was raised to 85°C. While stirring the inside of the polymerization vessel at 600 rpm, propylene was continuously supplied at 240 liter/hr to saturate the liquid phase and the gas phase. Then, while continuously supplying propylene, 5.0 mL (7.5 mmol) of a toluene solution (1.5 mol/L) of methylaluminoxane (also referred to as DMAO) was added, and then dimethylsilylbis(2-methyl-4-fini). 6.0 mL (0.012 mmol) of a toluene solution of ruindenyl)zirconium dichloride (0.0020 mol/L) was added, and polymerization was carried out at 85° C. for 30 minutes under normal pressure. The termination of the polymerization was carried out by adding a small amount of isobutanol. The obtained polymerization reaction liquid was added to 5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80° C. for 10 hours to obtain 63.4 g of a propylene polymer (terminal unsaturated polypropylene (M-1)). When the obtained polymer was analyzed, the amount of unsaturated terminals was 0.88 per 1000 carbon atoms, and the amount of terminal vinyl was 0.69 per 1000 carbon atoms. The weight average molecular weight was 22,000 in terms of polypropylene.

Step (B): Production of Olefin Resin (β-1) The compound (1) represented by the following formula and used as a catalyst was synthesized by a known method.
After putting 10 g of terminal unsaturated polypropylene (M-1) and 500 ml of xylene into a glass reactor having an internal volume of 1 L that was sufficiently replaced with nitrogen, the temperature was raised to 97° C. to dissolve the terminal unsaturated polypropylene (M-1). Let While stirring the inside of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously supplied at 120 liter/hr and 15.6 liter/hr, respectively, to saturate the liquid phase and the gas phase. Then, in a state where ethylene and 1-butene were continuously supplied, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol/L) of triisobutylaluminum (also referred to as iBu ₃ Al) was added to the compound (1). 5.0 mL (0.01 mmol) of a toluene solution (0.0020 mol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as Ph ₃ CB(C ₆ F ₅ ) ₄ ) in toluene solution ( 6.25 mL (0.025 mmol) of 4.0 mmol/L) was added, and polymerization was performed at 97° C. for 40 minutes under normal pressure. The termination of the polymerization was carried out by adding a small amount of isobutanol. The obtained polymerization reaction liquid was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80° C. for 10 hours to obtain 32.9 g of an olefin resin (β-1). When the obtained resin was analyzed, the ratio P was 30.4 wt %, the ratio E was 19.5 wt %, the a value was 2.6, the melting peak Tm was 130.6° C. above 120° C., and the heat of fusion ΔH was 25.1 J/g, glass transition temperature Tg is -68.0°C, intrinsic viscosity [η] is 2.1 dl/g, the proportion of repeating units derived from ethylene is 59.8 mol%, ortho-dichlorobenzene of 50 degrees or less. The soluble component was 22.7 wt %. Furthermore, when a resin obtained by the same polymerization except that the terminal unsaturated polypropylene (M-1) was not added in the production of the olefin resin (β-1) was analyzed by the method described above, 1-butene The ratio was 19.4 mol%, the weight average molecular weight was 140,000 g/mol, and the intrinsic viscosity [η] was 2.2 dl/g, which is a copolymer constituting the main chain of the olefin resin (β-1). And

(Production of olefin resin (γ-1))
500 ml of xylene was placed in a glass reactor having an internal volume of 1 L that had been sufficiently replaced with nitrogen, and then the temperature was raised to 97°C. While stirring the inside of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously supplied at 120 liter/hr and 15.6 liter/hr, respectively, to saturate the liquid phase and the gas phase. Then, in a state where ethylene and 1-butene were continuously supplied, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol/L) of triisobutylaluminum (also referred to as iBu ₃ Al) was added to the compound (1). 5.0 mL (0.01 mmol) of a toluene solution (0.0020 mol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as Ph ₃ CB(C ₆ F ₅ ) ₄ ) in toluene solution ( 6.25 mL (0.025 mmol) of 4.0 mmol/L) was added, and polymerization was performed at 97° C. for 40 minutes under normal pressure. The termination of the polymerization was carried out by adding a small amount of isobutanol. The obtained polymerization reaction liquid was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80° C. for 10 hours to obtain 23.0 g of an olefin resin (γ-1). When the obtained resin was analyzed, the glass transition temperature Tg was −68.0° C., the intrinsic viscosity [η] was 2.2 dl/g, the MFR was 0.01 g/10 min, and the ratio of 1-butene was 19.4 mol %. Was a copolymer of ethylene and 1-butene.

(Production of olefin resin (γ-2))
23 L/hr of dehydrated hexane and 0 of the compound (2) were placed in a stainless steel polymerization vessel having an internal volume of 100 L equipped with a stirring blade (stirring speed=250 rpm, internal temperature 110° C., polymerization pressure 1.0 MPa·G). .0053 mmol/hr, triphenylcarbenium tetrakis(pentafluorophenyl)borate 0.021 mmol/hr and triisobutylaluminum 2.2 ml/hr were continuously supplied, and the gas composition in the gas phase polymerization vessel was changed. , Butene/ethylene is 0.23 (molar ratio), and hydrogen/ethylene is 0.017 (molar ratio), butene, ethylene, and hydrogen are continuously supplied, and the produced polymerization liquid is fed to the side wall of the polymerization vessel. Through the provided outlet, the solution was continuously discharged while adjusting the opening of the liquid level control valve so as to maintain 28 L of the solution in the polymerization vessel. The resulting polymerization solution was introduced into a heater and heated to 180° C., and as a catalyst deactivator, 80 mL of methanol was added every hour to stop the polymerization, and the polymerization solution was continuously transferred to a devolatization step under reduced pressure for drying. By doing so, an olefin resin (γ-2) was obtained at a production rate of 2.1 kg/hr. When the obtained resin was analyzed, the glass transition temperature Tg was −65.2° C., the intrinsic viscosity [η] was 2.6 dl/g, the MFR was 0.2 g/10 min, and the ratio of 1-butene was 19.0 mol %. Was a copolymer of ethylene and 1-butene.

(Production of propylene-based resin composition)
70 parts by weight of the propylene resin (α-1), 24 parts by weight of the olefin resin (β-1), and 6 parts by weight of the olefin resin (γ-1) as described in the formulation of Example 1 shown in Table 1. Part, a heat-resistant stabilizer IRGANOX1010 (trademark of Ciba-Geigy Co., Ltd.) 0.1 part by weight, and a heat-resistant stabilizer IRGAFOS168 (trademark of Ciba-Geigy Co., Ltd.) 0.1 part by weight, and melt-kneaded under the following conditions at 210° C. Using the hydraulic heat press machine set to 1, after molding for 9 minutes, after molding for 3 minutes under pressure of 10 MPa, it is a propylene-based resin composition by cooling for 3 minutes under pressure of 10 MPa at 20°C. Created a press sheet. The physical properties of the obtained pressed sheet were measured by the methods described above. The results are shown in Table 1.
<Melting and kneading conditions>
Kneading machine: Labo Plastomill manufactured by Toyo Seiki Co., Ltd. (2-axis batch type melt kneading device)
Kneading temperature: 190℃
Screw rotation speed: 50 rpm
Kneading time: 5 minutes Resin amount: 50g

[Example 2]
Except that the propylene-based resin (α-1), the olefin-based resin (β-1), and the olefin-based resin (γ-1) were melt-kneaded in accordance with the formulation of Example 2 shown in Table 1. The same procedure as in 1 was performed.

[Example 3]
Except that the propylene resin (α-1), the olefin resin (β-1), and the olefin resin (γ-1) were melt-kneaded in accordance with the formulation of Example 3 shown in Table 1. The same procedure as in 1 was performed.

[Example 4]
Example except that the propylene resin (α-1), the olefin resin (β-1), and the olefin resin (γ-2) were melt-kneaded according to the formulation of Example 4 shown in Table 1. The same procedure as in 1 was performed.

[Example 5]
According to the formulation of Example 5 shown in Table 1, except that the propylene resin (α-1), the olefin resin (β-1), and the olefin resin (γ-2) were melt-kneaded. The same procedure as in 1 was performed.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that the propylene resin (α-1) and the olefin resin (β-1) were melt-kneaded according to the formulation of Comparative Example 1 shown in Table 1.

[Comparative example 2]
The same procedure as in Example 1 was carried out except that the propylene resin (α-1) and the olefin resin (β-1) were melt-kneaded according to the formulation of Comparative Example 2 shown in Table 1.

[Comparative Example 3]
Example 1 was repeated except that the propylene resin (α-1) and the olefin resin (γ-1) were melt-kneaded according to the formulation of Comparative Example 3 shown in Table 1.

[Comparative Example 4]
The same procedure as in Example 1 was carried out except that the propylene resin (α-1) and the olefin resin (γ-1) were melt-kneaded according to the formulation of Comparative Example 4 shown in Table 1.

(Comparison between Example and Comparative Example)
In FIG. 1, the effect of modifying impact resistance at room temperature was compared in terms of balance between tensile elastic modulus and high-speed impact strength. Examples 1 to 5 show a balance of rigidity and impact resistance equal to or higher than that of Comparative Examples 1 and 2 although the amount of the olefin resin (β) is smaller than that of Comparative Examples 1 and 2. Further, Examples 1 to 5 exhibit sufficiently excellent impact resistance modification performance as compared with Comparative Examples 3 to 4 not containing the olefin resin β.

In FIG. 2, the effect of modifying the impact resistance at low temperature was compared by the balance between the Izod impact strength at −40° C. and the tensile elastic modulus.
Examples 1 to 5 show the same balance of rigidity and impact resistance even though the blending amount of the olefin resin (β) is smaller than that of Comparative Examples 1 and 2. Further, Examples 1 to 5 exhibit sufficiently excellent impact resistance modification performance as compared with Comparative Examples 3 to 4 not containing the olefin resin β.

Claims (4)

Propylene resin (α), olefin resin (β) satisfying the following requirements (β-I) to (β-VI), and olefin resin ((γ-I) to (γ-III) satisfying the following requirements ( (gamma)) is contained, The propylene resin composition characterized by the above-mentioned.
The (β-I) olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene/α-olefin copolymer and a side chain made of a propylene polymer.
(Β-II) When the proportion of the propylene polymer contained in the olefin resin (β) is Pwt%, P is in the range of 5 to 60.
(Β-III) The proportion of the component having a peak value of the differential elution curve of less than 65° C. measured by a cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent to the olefin resin (β) is Ewt%. Then, the value a represented by the following relational expression (Eq-1) is 1.4 or more.

(Β-IV) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165°C, and the glass transition temperature (Tg) is in the range of -80 to -30°C.
(Β-V) Thermal xylene insoluble amount is less than 3 wt %.
(Β-VI) The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 0.5 to 5.0 dl/g.
(Γ-I) The olefin resin (γ) is an ethylene/α-olefin copolymer.
(Γ-II) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30°C.
(Γ-III) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 5.0 dl/g. When the total content of the propylene resin (α), the olefin resin (β) and the olefin resin (γ) is 100 parts by weight, the content of the propylene resin (α) is 50 to 90 parts by weight. The propylene resin composition according to claim 1, wherein the propylene resin composition is present. The propylene resin composition according to claim 1 or 2, wherein the weight ratio ((β)/(γ)) of the olefin resin (β) and the olefin resin (γ) is in the range of 95/5 to 5/95. Stuff. The propylene resin composition according to any one of claims 1 to 3, wherein the olefin resin (β) is obtained by a production method including the following steps (A) and (B).
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce an unsaturated terminal polypropylene. Step (B) In the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the following general formula [B], the unsaturated terminal polypropylene produced in step (A), ethylene, and 3 to 3 carbon atoms. Copolymerizing with at least one α-olefin selected from 20 α-olefins

(In the formula [B], each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group or a silicon-containing group. A hetero atom-containing group is shown, and two adjacent groups of R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom and a hydrocarbon. The same atom or the same group selected from a group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may combine with each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anion ligand or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

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