JP6564289B2 - Olefinic resin, production method and composition thereof, and molded article - Google Patents

Description

  The present invention includes a resin comprising a graft polymer having an ethylene polymer and a propylene polymer in the side chain and the main chain comprising an ethylene copolymer, a method for producing the resin, and the resin The present invention relates to a resin composition and a molded body obtained from the composition.

  Polyolefin resins such as polyethylene and polypropylene are low in production energy, light weight, and excellent in recyclability, so to 3R (Reduce, Reuse, Recycle) to form a recycling society in each industry. Attention is growing in the efforts. Polyolefin resins are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, etc. One type of polymer may be used alone. However, it is used as a resin composition containing a plurality of resins depending on the required performance.

For example, in an automobile member, it is used as a composition containing an elastomer in a propylene-based resin so that sufficient rigidity and impact resistance can be obtained even if the molded product is reduced in weight and thickness.
As one of the methodologies for improving the physical properties of such an olefin resin, a block polymer or graft polymer technology in which polyolefin resins having different structures are chemically bonded has been the object of development. As a technique related to such a polymer, there are a method of chemically reacting different polymers with each other and a method of generating them in a polymerization step, and the present technology relates to the latter.

  Among polymer chains composed of different polymer chains, a polymer chain in which a crystal chain and an amorphous chain are combined is particularly noted. It is expected that the mechanical properties such as rigidity, mechanical strength, and heat resistance of the crystal chain and the polymer properties that conflict with each other such as the flexibility, resin modification property, and adhesiveness of the amorphous chain are expected. Therefore, various techniques described later are disclosed.

  First, as a technique for producing an olefinic block copolymer composed of a crystalline polyethylene chain and an amorphous polymer chain, a living polymerization method can be mentioned as a representative example. Patent Document 1 and Patent Document 2 disclose a technique for producing a linear block polymer in which a polyethylene crystal chain and an amorphous chain of an ethylene elastomer are linked using a Group 4 metal complex catalyst having living polymerizability. . Patent Documents 3 and 4 disclose a technique related to a multi-block polymer using a reversible chain transfer reaction that acts between two kinds of transition metal catalysts. On the other hand, Patent Documents 5 to 11 are disclosed as techniques for producing a block copolymer composed of a crystalline polypropylene chain and an amorphous polymer chain.

  Patent Document 5 relates to a technique for forming a linear block polymer of a crystalline polypropylene chain and an amorphous olefin polymer chain by applying the above-described reversible chain transfer reaction to a series multistage polymerization tank.

  On the other hand, Patent Documents 6 to 11 relate to a technique for producing a graft-type olefin polymer having an amorphous polymer chain as a main chain and a crystalline polypropylene chain as a side chain. These are techniques involving multistage polymerization in which a specific metallocene catalyst is used to produce crystalline polypropylene having a vinyl group at the terminal, and these are then copolymerized with various olefin monomers.

  In any of these literatures on grafted polymers having crystal chains and amorphous chains, polyethylene chains or polypropylene chains are applied as crystalline polymer chains, but specific measures for polymers having both are shown. It has not been.

International Publication No. 2001/055231 JP 2004-204057 A International Publication No. 2005/090426 International Publication No. 2005/090427 JP 2013-529705 A JP 2001-525460 A JP 2001-527589 A JP 2001-525463 A JP 2008-144152 A JP 2009-114404 A International Publication No. 2013/061974

  Thermoplastic resin that has heat resistance and flexibility, has excellent compatibility with both polyethylene resin and polypropylene resin, and can be suitably used as a modifier that effectively acts on various polyolefins To provide.

  In addition, according to the study by the present inventors, conventional ethylene / α-olefin copolymers and graft polymers having a propylene-based polymer in the side chain have pellets or molded products obtained depending on the composition. Sticky problems are recognized, and reduction of stickiness is also an issue.

  As a result of intensive studies to solve the above problems, the present inventors have developed a resin containing a graft type polymer composed of an ethylene copolymer having an ethylene polymer and a propylene polymer in the side chain. The resin made of the graft polymer is applicable to general polyolefin molding methods because it exhibits thermoplasticity, and further, as a resin modifier because of its excellent compatibility with polyethylene resins and polypropylene resins. The present inventors have found that it is suitable as a wide range of compound resin raw materials. Furthermore, it has been found that the stickiness problem is also solved by the resin.

That is, the present invention relates to the following [1] to [14], for example.
[1] It has a main chain (MC) composed of an ethylene / α-olefin copolymer, a side chain (SE) composed of an ethylene polymer, and a side chain (SP) composed of a propylene polymer. An olefin resin (β) that includes the graft polymer [R1] and satisfies the following requirement (I).
(I) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5 dl / g.

[2] The olefin resin (β) according to [1], which satisfies the following requirement (II).
(II) In differential scanning calorimetry, a melting point (Tm) is observed in the range of 80 to 170 ° C.

[3] The olefin resin (β) according to [1] or [2], which satisfies the following requirement (III).
(III) The glass transition temperature (Tg) measured with a differential scanning calorimeter is in the range of −80 to −30 ° C.

[4] The olefin resin (β) according to any one of [1] to [3], which satisfies the following requirement (IV).
(IV) The proportion of repeating units derived from ethylene is in the range of 10 to 80 mol% with respect to all repeating units, and the proportion of repeating units derived from propylene is in the range of 2 to 80 mol% with respect to all repeating units.

[5] The olefin resin (β) according to any one of [1] to [4], wherein the graft polymer [R1] satisfies the following requirement (i).
(I) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain (SP) is 93% or more.

[6] The olefin resin (β) according to any one of [1] to [5], wherein the graft polymer [R1] satisfies at least one of the following requirements (ii) or (iii).
(Ii) The ethylene / α-olefin copolymer constituting the main chain (MC) has a repeating unit derived from ethylene and at least one α selected from α-olefins having 3 to 20 carbon atoms. -It has a repeating unit derived from an olefin in the range of 5 to 50 mol% in the main chain (MC).
(Iii) The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain (MC) is 10,000 to 500,000.

[7] The olefin resin (β) according to any one of [1] to [6], wherein the graft polymer [R1] satisfies the following requirements (iv) to (vii).
(Iv) The ethylene polymer constituting the side chain (SE) has a repeating unit derived from ethylene in the range of 95 to 100 mol% in the side chain (SE), and an α-olefin having 3 to 20 carbon atoms. In the side chain (SE) in the range of 0 to 5 mol%.
(V) The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1,000 to 30,000.
(Vi) The propylene-based polymer constituting the side chain (SP) has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain (SP), and ethylene and α having 4 to 20 carbon atoms. -It has a repeating unit derived from at least one α-olefin selected from olefins in the range of 0 to 5 mol% in the side chain (SP).
(Vii) The propylene-based polymer constituting the side chain (SP) has a weight average molecular weight of 5,000 to 100,000.

  [8] The method for producing an olefin resin (β) according to any one of [1] to [7], wherein two or more transition metal compounds are used.

[9] The method for producing an olefin resin (β) according to [8], comprising the following steps (A), (B) and (C).
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process (B) The process of superposing | polymerizing ethylene in presence of the catalyst for olefin polymerization containing the transition metal compound [B] of the periodic table group 4 or 5 which has an organic ligand, and manufacturing terminal unsaturated polyethylene ( C) terminal unsaturated polypropylene produced in step (B) and terminal unsaturated polypropylene produced in step (B) in the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table. A step of copolymerizing polyethylene, ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms.

  [10] 2 to 98 parts by mass of the propylene resin (α-1) and 2 to 98 parts by mass of the olefin resin (β) according to any one of [1] to [7] (propylene resin (α-1 ) And the olefin resin (β) as 100 parts by mass).

  [11] 50 to 98 parts by mass of the propylene resin (α-1) and 2 to 50 parts by mass of the olefin resin (β) (total of the propylene resin (α-1) and the olefin resin (β) The propylene-based resin composition according to [10], wherein the propylene-based resin composition is 100 parts by mass).

  [12] 2 to 98 parts by mass of ethylene resin (α-2) and 2 to 98 parts by mass of olefin resin (β) according to any one of [1] to [7] (ethylene resin (α-2 ) And the olefin resin (β) as 100 parts by mass).

  [13] A resin comprising a propylene resin (α-1), an ethylene resin (α-2), and the olefin resin (β) according to any one of [1] to [7]. Composition.

  [14] A molded product obtained from the resin composition according to any one of [10] to [13].

  The olefin resin of the present invention has heat resistance and flexibility, is excellent in compatibility with both polyethylene resin and polypropylene resin, and is also suitable as a modifier that effectively acts on various polyolefins. It can be used, has thermoplasticity, and has reduced stickiness.

Hereinafter, the olefin resin (β), the method for producing the olefin resin (β), the resin composition, and the molded body of the present invention will be described in detail.
<Olefin resin (β)>
The olefin resin (β) of the present invention is composed of a main chain (MC) composed of an ethylene / α-olefin copolymer, a side chain (SE) composed of an ethylene polymer, and a propylene polymer. The graft polymer [R1] having a side chain (SP) that satisfies the following requirements (I) is satisfied.

  The olefin resin (β) preferably satisfies the following requirement (II), preferably satisfies the following requirement (III), and preferably satisfies the following requirement (IV). That is, the olefin resin (β) preferably satisfies one or more of the following requirements (II) to (IV), more preferably satisfies two or more, and most preferably satisfies three.

  The olefin resin (β) may be composed of only the graft polymer [R1], or may be composed of the graft polymer [R1] and one or more other olefin polymers. May be. The graft polymer [R1] constituting the olefin resin (β) may be one kind of polymer or two or more kinds of polymers.

  The olefin resin (β) may contain components other than the graft polymer [R1]. According to the production method described later, a part of the terminal unsaturated polypropylene produced in the step (A) and the terminal unsaturated polyethylene produced in the step (B) are copolymerized in the step (C) to be graft type. Although constituting the side chain of the polymer [R1], a part does not contribute to the copolymerization in the step (C), that is, it does not become the side chain of the graft polymer [R1], but the olefin resin (β) Can be included. In the entire olefin resin (β), the proportion of the graft polymer [R1] is preferably 5 to 95% by mass, more preferably 10 to 80% by mass.

(I) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5 dl / g.
(II) In differential scanning calorimetry, a melting point (Tm) is observed in the range of 80 to 170 ° C.
(III) The glass transition temperature (Tg) measured with a differential scanning calorimeter is in the range of −80 to −30 ° C.
(IV) The proportion of repeating units derived from ethylene is in the range of 10 to 80 mol% with respect to all repeating units, and the proportion of repeating units derived from propylene is in the range of 2 to 80 mol% with respect to all repeating units.

Hereinafter, the graft polymer [R1] and the above requirements (I) to (IV) will be specifically described.
[Graft polymer [R1]]
The olefin resin (β) contains the graft polymer [R1] as an essential component. The graft polymer [R1] is composed of a main chain (MC) composed of an ethylene / α-olefin copolymer, a side chain (SE) composed of an ethylene polymer, and a propylene polymer. It is a graft polymer having a side chain (SP).

  In the present invention, the term “graft polymer” is a polymer in which one or more side chains are bonded to the main chain. The graft polymer [R1] is a polymer in which one or more side chains (SE) are bonded and one or more side chains (SP) are bonded to the main chain (MC).

  The graft polymer [R1] is composed of an ethylene / α-olefin copolymer main chain (MC), an ethylene polymer side chain (SE), and a propylene polymer side chain. Since (SE) has a chemically bonded structure, the olefin resin (β) containing the graft polymer [R1] is a propylene resin or ethylene resin containing a linear ethylene polymer. Compared with high compatibility. For this reason, the resin composition containing an olefin resin (β) and a propylene resin (α-1) or an ethylene resin (α-2) described later can exhibit a very excellent balance of physical properties.

  Further, since the olefin resin (β) contains the graft polymer [R1] having the above structure, it has excellent compatibility with a polyethylene resin and a polypropylene resin, and further has a feature that stickiness is suppressed.

As described above, the graft polymer [R1] is a graft copolymer having a main chain (MC) and side chains (SP and SE).
The graft polymer [R1] preferably satisfies the following requirement (i). The graft polymer [R1] preferably satisfies at least one of the following requirements (ii) or (iii), and preferably satisfies the requirements (ii) and (iii). The graft polymer [R1] preferably satisfies at least one of the following requirements (iv) to (vii), more preferably satisfies at least two, and further preferably satisfies at least three. It is particularly preferable to satisfy one of the requirements, that is, satisfy the requirements (iv) to (vii).

  (I) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain (SP) is 93% or more.

  (Ii) The ethylene / α-olefin copolymer constituting the main chain (MC) has a repeating unit derived from ethylene and at least one α selected from α-olefins having 3 to 20 carbon atoms. -It has a repeating unit derived from an olefin in the range of 5 to 50 mol% in the main chain (MC).

  (Iii) The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain (MC) is 10,000 to 500,000.

  (Iv) The ethylene polymer constituting the side chain (SE) has a repeating unit derived from ethylene in the range of 95 to 100 mol% in the side chain (SE), and an α-olefin having 3 to 20 carbon atoms. In the side chain (SE) in the range of 0 to 5 mol%.

  (V) The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1,000 to 30,000.

  (Vi) The propylene-based polymer constituting the side chain (SP) has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain (SP), and ethylene and α having 4 to 20 carbon atoms. -It has a repeating unit derived from at least one α-olefin selected from olefins in the range of 0 to 5 mol% in the side chain (SP).

(Vii) The propylene-based polymer constituting the side chain (SP) has a weight average molecular weight of 5,000 to 100,000.
Hereinafter, these requirements (i) to (vii) will be specifically described.

[Requirement (i)]
In the graft polymer [R1], the isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain (SP) is 93% or more.

  Since the side chain (SP) of the graft polymer [R1] has the above characteristics, the side chain exhibits crystallinity and has a melting point. When the side chain (SP) of the graft polymer [R1] is an isotactic polypropylene polymer having a high melting point, the heat resistance of the olefin resin (β) is enhanced. Furthermore, the fact that the side chain of the graft polymer [R1] is an isotactic polypropylene polymer increases the compatibility of the olefin resin (β) with the propylene resin. For this reason, since the obtained propylene-type resin composition can maintain favorable rigidity and hardness, expressing favorable impact resistance, it is preferable.

  The graft polymer [R1] is a terminal unsaturated polypropylene produced in the step (A) and a terminal unsaturated polyethylene produced in the step (B) in the production step (C) of the olefin resin (β) described later. It can be obtained by copolymerizing ethylene and α-olefin. That is, the composition and stereoregularity of the terminal unsaturated polypropylene correspond to the composition and stereoregularity of the side chain (SP) of the graft polymer [R1]. Therefore, the composition and stereoregularity of the terminal unsaturated polypropylene produced in the step (A) are calculated using a known method, and the composition and stereoregularity are calculated based on the composition of the side chain (SP) of the graft polymer [R1]. And stereoregularity.

[Requirement (ii)]
The ethylene / α-olefin copolymer constituting the main chain (MC) has at least one α-olefin having a repeating unit derived from ethylene and selected from α-olefins having 3 to 20 carbon atoms. It has the derived repeating unit in the range of 5 to 50 mol% in the main chain (MC).

  The main chain (MC) of the graft-type polymer [R1] is composed of an ethylene / α-olefin copolymer. In the graft-type polymer [R1], flexibility, low temperature characteristics required as a modifier, etc. It becomes the part that bears the characteristics. In order to ensure such properties, the main chain of the graft polymer [R1] is at least one α-olefin selected from a repeating unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. It consists of repeating units derived from

  Here, specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, and 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 given.

  The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Examples thereof include branched olefins such as 3-methyl-1-butene, among which propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene, 1-pentene and 1-hexene are preferable. 1-octene is more preferable. By using 1-butene, 1-pentene, 1-hexene, or 1-octene as an α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene, the physical property balance between rigidity and impact resistance is most favorable. A propylene resin composition or an ethylene resin composition is obtained.

  The proportion of the repeating unit derived from ethylene in the ethylene / α-olefin copolymer constituting the main chain of the graft polymer [R1] is preferably 50 to 95 mol%, more preferably 60 to 90 mol in the main chain. %, More preferably in the range of 65 to 85 mol%. The proportion of the repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms is preferably 5 to 50 mol%, more preferably 10 to 40 mol% in the main chain, More preferably, it is the range of 15-35 mol%. “In the main chain” means a ratio when the total repeating unit contained in the main chain is 100 mol%.

  Since the ratio of the repeating unit derived from ethylene and α-olefin in the main chain is in the above range, the olefin resin (β) is rich in flexibility and excellent in low temperature characteristics. ) Is excellent in low-temperature impact resistance. On the other hand, when the repeating unit derived from α-olefin is less than 5 mol%, the resulting olefin resin is inferior in flexibility and low-temperature characteristics, and therefore the resin composition containing the resin is inferior in low-temperature impact resistance. There is.

  The molar ratio of the 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.

  In addition, the molar ratio (mol%) of the repeating unit derived from ethylene contained in the main chain and the repeating unit derived from α-olefin is, for example, ethylene · α obtained under a condition not containing terminal unsaturated polypropylene described later. -It calculates | requires from calculating | requiring the alpha-olefin composition of an olefin copolymer by a conventional method, and deducting the influence derived from a terminal unsaturated polypropylene and a side chain from the alpha-olefin composition of an olefin resin ((beta)).

[Requirements (iii)]
The ethylene / α-olefin copolymer constituting the main chain (MC) of the graft polymer [R1] has a weight average molecular weight of 10,000 to 500,000. In the resin composition of the present invention, in order to improve the moldability (fluidity) of the resin while maintaining the mechanical strength, it is preferably in the range of 10,000 to 500,000, preferably 50,000 to 200,000. More preferably, it is in the range of 000. The weight average molecular weight is a polyethylene-converted weight average molecular weight determined by gel permeation chromatography (GPC).

  When the weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft polymer [R1] is in the above range, the propylene resin composition or ethylene resin composition containing the olefin resin (β). Objects tend to have a better balance of impact resistance, stiffness and toughness. On the other hand, if the weight average molecular weight is less than 10,000, impact resistance and toughness are lowered, and if it is more than 500,000, dispersion in propylene-based resin or polyethylene-based resin occurs and a desired physical property balance is obtained. May be difficult.

  The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain (MC) of the graft polymer [R1] is controlled by controlling the ethylene concentration in the polymerization system in the production step (C) described later. Can be adjusted. Examples of the ethylene concentration control method include adjustment of ethylene partial pressure and polymerization temperature. 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 of the ethylene / α-olefin copolymer constituting the main chain is, for example, an ethylene / α-olefin copolymer produced under the conditions that do not include terminal unsaturated polypropylene and terminal unsaturated polyethylene described later. Or by analyzing the olefin-based resin (β) and subtracting the effects derived from terminal unsaturated polypropylene, terminal unsaturated polyethylene, side chain (SP) and side chain (SE).

[Requirement (iv)]
The ethylene polymer constituting the side chain (SE) has a repeating unit derived from ethylene in the range of 95 to 100 mol% in the side chain (SE), and is selected from α-olefins having 3 to 20 carbon atoms. It has a repeating unit derived from at least one α-olefin in the range of 0 to 5 mol% in the side chain (SE).

  The repeating unit derived from ethylene is more preferably 98 to 100 mol%, more preferably in the range of 99.5 to 100 mol%, and the repeating unit derived from α-olefin is further preferably 0 to 2 mol%, more preferably 0 to 0 mol%. 0.5 mol%. By being in the said range, it becomes a crystalline ethylene polymer chain, is excellent in compatibility with polyethylene resin, and stickiness is suppressed. Note that “in the side chain (SE)” means a ratio when all the repeating units contained in the side chain (SE) (ethylene-based polymer) are 100 mol%.

[Requirement (v)]
The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1,000 to 30,000. More preferably, it is the range of 2,000-10,000.

  When the weight average molecular weight of the side chain (SE) is below the above range, the melting point of the crystalline component consisting of the ethylene polymer portion in the olefin polymer [R1] is lowered, the heat resistance is lowered, and the crystalline component is reduced. Due to the weakening of the physical cross-linking points formed, there is a risk that the polymer will be inferior in mechanical properties.

  On the other hand, if the weight average molecular weight of the side chain (SE) exceeds the above range, the relative amount of the amorphous or low crystalline component consisting of the ethylene / α-olefin copolymer portion corresponding to the main chain (MC) decreases. There is a possibility that flexibility as a whole cannot be secured.

  The weight average molecular weight of the side chain (SE) is generated in GPC analysis of a pre-synthesized ethylene polymer portion (macromonomer) corresponding to the side chain (SE), that is, in the step (B). It is the weight average molecular weight of polyethylene conversion calculated | required by measuring the weight average molecular weight of terminal unsaturated polyethylene by GPC.

  Examples of the adjustment of the weight average molecular weight of the side chain (SE) include a method of changing the type of transition metal compound used for the vinyl-terminated macromonomer production catalyst described later, and a method of adjusting the polymerization conditions.

[Requirement (vi)]
The propylene-based polymer constituting the side chain (SP) of the graft polymer [R1] has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain (SP), and contains ethylene and carbon atoms. It has a repeating unit derived from at least one α-olefin selected from 4 to 20 α-olefins in the range of 0 to 5 mol% in the side chain (SP).

  The repeating unit derived from propylene more preferably has a range of 99.5 to 100 mol%, and is a repeating unit derived from at least one α-olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms. In the range of 0 to 0.5 mol%. Note that “in the side chain (SP)” means a ratio when the total repeating unit contained in the side chain (SP) (propylene polymer) is 100 mol%.

[Requirements (vii)]
The propylene-based polymer constituting the side chain (SP) has a weight average molecular weight of 5,000 to 100,000. The weight average molecular weight is preferably in the range of 5,000 to 60,000, more preferably 5,000 to 25,000.

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

  When the weight average molecular weight of the propylene polymer constituting the side chain (SP) of the graft polymer [R1] is less than 5,000, the interfacial strength with the propylene resin is weakened, and the elongation of the propylene resin composition is increased. And impact resistance may be reduced.

  When the weight average molecular weight of the propylene polymer constituting the side chain (SP) of the graft polymer [R1] is greater than 100,000, the fluidity during molding of the resin composition containing the olefin resin (β) is high. It may worsen and cause deterioration of workability. In addition, the compatibility between the propylene resin and the olefin resin (β) decreases, and the tensile elongation and impact resistance of the propylene resin composition containing the propylene resin and the olefin resin (β) decrease. In some cases, the surface hardness of the molded body obtained from the propylene-based resin composition is lowered.

In addition, the weight average molecular weight of the propylene-type polymer which comprises a side chain (SP) can be calculated | required by measuring the weight average molecular weight of the terminal unsaturated polypropylene produced | generated at a process (A) by a conventional method. For example, the weight average molecular weight in terms of polypropylene of the terminal unsaturated polypropylene determined 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-based polymer constituting the side chain (SP) include a method of adjusting the polymerization temperature and the polymerization pressure in the production step (A) described later.

[Requirement (I)]
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 resin composition containing the olefin resin (β) has not only impact resistance but also good rigidity and mechanical strength, and further good moldability. Also have.

[Requirement (II)]
The melting point (Tm) of the olefin resin (β) is observed in the range of 80 to 170 ° C. in the differential scanning calorimetry (DSC).
That is, the olefin resin (β) has a melting peak measured by differential scanning calorimetry (DSC) in the range of 80 to 170 ° C.

  There may be a plurality of melting peaks observed in the range of 80 to 170 ° C. In that case, the melting point due to the side chain (SE) of the graft polymer [R1] constituting the olefin resin (β) It is considered that the melting point due to the side chain (SP) and, in some cases, the melting point due to the main chain (MC) are observed.

  The temperature at which the melting peak appears, that is, the melting point (Tm), is obtained by melting the sample once by DSC in the heating step and then crystallizing it by the cooling step to 30 ° C. This is an analysis of the endothermic peak that appears at (° C./min).

  The melting point due to the side chain (SE) is usually observed in the range of 80 to 130 ° C. By being in this range, the olefin resin (β) can be compatible with the polyethylene resin, and as a result, the olefin resin (β) and the ethylene resin composition have rigidity, heat resistance and toughness. The balance becomes better. Moreover, it is thought that the effect which suppresses stickiness of resin is acquired by having the said property derived from the side chain (SE) of graft type polymer [R1] in an olefin resin ((beta)). Examples of a method for adjusting the melting point due to the side chain (SE) to the above range include a method for adjusting the polymerization temperature and the polymerization pressure in the production step (B) described later.

  The melting point due to the side chain (SP) is usually observed in the range of 100 to 170 ° C. By being in this range, the olefin resin (β) can be well compatible with the propylene resin, and as a result, the propylene resin composition containing the olefin resin (β) and the propylene polymer is The balance of rigidity, heat resistance and toughness is improved. As a method of adjusting the melting point due to the side chain (SP) to the above range, a method of adjusting the polymerization temperature and polymerization pressure in the production step (A) described later can be mentioned.

In the differential scanning calorimetry (DSC), the olefin resin (β) has a melting point (Tm ₁ ) in the range of 80 to 130 ° C. and a melting point (Tm ₂ ) in the range of 100 to 170 ° C. It is preferable. Note that Tm ₁ <Tm ₂ .

  Usually, the melting point due to the main chain (MC) is not observed by differential scanning calorimetry (DSC) or is observed in the range of 100 ° C. or lower. The melting point due to the main chain (MC) is adjusted by the amount of structural units derived from the α-olefin of the ethylene / α-olefin copolymer constituting the main chain (MC).

[Requirement (III)]
The olefin resin (β) has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) in the range of −80 to −30 ° C. Tg is preferably in the range of −80 to −40 ° C., more preferably −70 to −50 ° C.

  The glass transition temperature (Tg) is mainly attributed to the properties of the ethylene / α-olefin copolymer constituting the main chain (MC) of the graft polymer [R1]. When the glass transition temperature (Tg) is in the range of −80 to −30 ° C., the propylene resin composition containing the olefin resin (β) exhibits excellent impact resistance.

  The glass transition temperature (Tg) in the above range can be obtained by controlling the type and composition of the α-olefin structural unit contained in the ethylene / α-olefin copolymer constituting the main chain (MC).

[Requirement (IV)]
In the olefin resin (β), the proportion of repeating units derived from ethylene is in the range of 10 to 80 mol% with respect to all repeating units, and the proportion of repeating units derived from propylene is 2 to 80 mol% with respect to all repeating units. Is in range.

  The proportion of repeating units derived from ethylene is preferably 20 to 80 mol%, more preferably 30 to 80 mol%, still more preferably 40 to 80 mol%, and particularly preferably 40 to 75 mol%.

  Furthermore, the ratio of the repeating unit derived from propylene is preferably 3 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 5 to 40 mol%.

When the repeating unit derived from ethylene and the repeating unit derived from propylene are in the above range, the ethylene / α-olefin copolymer, the ethylene polymer, and the propylene polymer are included in a balanced manner. The resin composition containing the base resin (β) has good impact resistance and elongation at break.
The olefin resin (β) preferably satisfies one or more of the following requirements (V) to (VII).

[Requirement (V)]
The proportion of the ethylene polymer contained in the olefin resin (β) is preferably 2 to 60% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass. When the ratio of the ethylene polymer is within the above range, the olefin resin (β) is considered to have an effect of suppressing the stickiness of the resin.

  Here, the ethylene polymer contained in the olefin resin (β) corresponds to a polymer or side chain derived from the terminal unsaturated polyethylene produced in the step (B) according to the production method described later, That is, the sum of the side chain (SE) copolymerized in the step (C) and the polyethylene linear polymer not taken into the main chain is shown.

  The ratio of the ethylene polymer contained in the olefin resin (β) is obtained from, for example, the ratio of the weight of the terminal unsaturated polyethylene used in the polymerization step (B) described later and the weight of the obtained olefin resin (β). It is done.

[Requirement (VI)]
The proportion of the propylene polymer contained in the olefin resin (β) is preferably 2 to 60% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass. When the proportion of the propylene polymer is within the above range, the olefin resin (β) can be well compatible with the propylene resin. As a result, the olefin resin (β) and the propylene polymer can be combined. The propylene-based resin composition to be contained has a good balance of rigidity, heat resistance and toughness.

  Here, the propylene polymer contained in the olefin resin (β) corresponds to a polymer or side chain derived from the terminal unsaturated polypropylene produced in the step (A) according to the production method described later, That is, the sum of the side chain (SP) copolymerized in the step (C) and the polypropylene linear polymer not taken into the main chain is shown.

  The proportion of the propylene polymer contained in the olefin resin (β) is determined from, for example, the ratio of the weight of the terminal unsaturated polypropylene used in the polymerization step (A) described later and the weight of the obtained olefin resin (β). It is done.

[Requirement (VII)]
The tensile elastic modulus of the olefin resin (β) based on ASTM D638 is preferably in the range of 2 to 400 MPa, more preferably 2 to 200 MPa. When the tensile modulus is in the above range, the olefin resin (β) is excellent in flexibility, and as a result, the resin composition containing the olefin resin (β) has good impact resistance and toughness.

The olefin 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 formed into a sheet having a thickness of 0.4 mm by hot pressing (180 ° C., heating for 5 minutes, cooling for 1 minute) and cut into pieces. About 100 mg is weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a sealed container. 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 formula.
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 heat xylene-insoluble amount at all or contains a small amount, so that it can be well dispersed in the propylene resin and the ethylene resin. The obtained resin composition exhibits a desired effect. On the other hand, if the thermal xylene insoluble part amount is 3 wt% or more, an appearance defect called “butsu” may occur in the molded article of the resin composition to be obtained.

  As shown in the production method described later, an olefin resin (β) having a thermal xylene-insoluble component in the above range can be obtained by adopting a method of directly obtaining the graft type polymer [R] 1 from the polymerization step. .

The olefin-based resin (β) preferably does not contain substances that cause coloring, off-flavor, and contamination of the final product.
Specific examples of substances that cause coloring, off-flavours, and contamination of the final product include heteroatom-containing compounds, and the heteroatom-containing compounds contain halogen atoms such as chlorine atoms and bromine atoms. Examples thereof include compounds, compounds containing chalcogen atoms such as acid atoms and sulfur atoms, and compounds containing pnictogen atoms such as nitrogen atoms and phosphorus atoms. Specific examples of the compound containing an oxygen atom include maleic anhydride and a maleic anhydride reactant.

  Examples of substances that cause coloring, off-flavor, and contamination of the final product include metal atom-containing compounds. Specifically, alkali metal-containing compounds such as sodium and potassium, alkaline earth such as magnesium and calcium, and the like. A metal-containing compound.

  In the olefin resin (β), the content of the hetero atom-containing compound is preferably 1000 ppm or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less. In the olefin resin (β), the content of the metal atom-containing compound is preferably 1000 ppm or less, more preferably 100 ppm or less, and still more preferably 10 ppm or less.

<Method for producing olefin resin (β)>
The olefin resin (β) is produced by, for example, a production method including the following steps (A), (B), and (C).

(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process (B) The process of superposing | polymerizing ethylene in presence of the catalyst for olefin polymerization containing the transition metal compound [B] of the periodic table group 4 or 5 which has an organic ligand, and manufacturing terminal unsaturated polyethylene ( C) terminal unsaturated polypropylene produced in step (B) and terminal unsaturated polypropylene produced in step (B) in the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table. Step of copolymerizing polyethylene, ethylene, and at least one α-olefin selected from α-olefin having 3 to 20 carbon atoms Hereinafter, steps (A), (B), and (C) are performed. Will be described in order.

[Process (A)]
Step (A) is a step of producing terminally unsaturated polypropylene as a raw material for the side chain (SP) composed of the propylene-based polymer [R1].

  In this step, propylene is polymerized in the presence of a catalyst for olefin polymerization containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. It is a process to do.

  In the present invention, the terminal unsaturated polypropylene means a polypropylene having terminal unsaturation represented by the following terminal structures (I) to (IV). “Poly” in the terminal structures (I) to (IV) represents a bonding position between the terminal structure and a propylene polymer molecular chain other than the terminal structure.

前記末端不飽和ポリプロピレンにおける末端不飽和の割合は１０００炭素原子あたり通常０．１〜６であるが、より好ましくは０．４〜３．０である。さらに、一般的に末端ビニルと呼ばれる末端構造（Ｉ）で表される末端不飽和割合は炭素原子１０００個あたり、通常０．１〜２．０個であるが、好ましくは、０．２〜２．０個の範囲にある。

The ratio of terminal unsaturation in the terminal unsaturated polypropylene is usually 0.1 to 6 per 1000 carbon atoms, more preferably 0.4 to 3.0. Further, the terminal unsaturation ratio represented by the terminal structure (I) generally called terminal vinyl is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.2 to 2 In the range of 0.

The terminal unsaturation is determined by determining the terminal structure of the terminal unsaturated polypropylene by ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The end 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), assuming that the integral value A of δ4.9 to 5.1 (2H) and the total integral value derived from the propylene-based polymer are B, the terminal structure (I) per 1000 carbon atoms Is obtained by the formula of 1000 × (A / 2) / (B / 2). When determining the ratio of other terminal structures, it should be replaced with the integrated value of the peak attributed to each structure while paying attention to the ratio of hydrogen.

  The proportion of terminal structure (I) in the terminal unsaturation is usually 30% or more, preferably 50% or more, more preferably 60% or more. The proportion of the terminal structure (I) in the terminal unsaturation described above is the sum of the numbers of the terminal structures (I) to (IV) existing per 1000 carbon atoms contained in the terminal unsaturated polypropylene. The ratio of the number of terminal structures (I) present per 1000 carbon atoms is expressed as a percentage.

The transition metal compound [A] functions as a polymerization catalyst for producing terminally unsaturated polypropylene in combination with the compound [D] described later.
As an olefin polymerization catalyst for producing terminally unsaturated polypropylene, Resconi, L .; Although known for a long time in JACS 1992, 114, 1025-1032, etc., the side chain of the olefin copolymer [R1] is isotactic or syndiotactic terminal unsaturated polypropylene, more preferably isotactic. Tic terminally unsaturated polypropylene is preferred.

  As the transition metal compound [A] contained in the olefin polymerization catalyst used for producing such a highly stereoregular polypropylene having a terminal structure (I) and a high content of terminal unsaturated polypropylene, a transition metal compound [A] can be used. The compounds disclosed in JP-A No. 1000579, JP-T-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443 and the like can be suitably used.

  More specifically, examples of the transition metal compound [A] include compounds selected from the group consisting of bridged bis (indenyl) zirconocenes or hafnocenes. More preferred 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 insertion reaction of terminal unsaturated polypropylene is suppressed, and olefin resin (β) and olefin resin The propylene-based resin composition containing the resin (β) 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) and the olefin resin (β) may impair physical properties such as rigidity. is there.

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

Step (A) can be carried out by any method 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 performed by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Of these, hexane is preferred from the viewpoint of reducing the load of the post-treatment process.

  In addition, the polymerization temperature in step (A) is usually in the range of 50 to 200 ° C, preferably in the range of 80 to 150 ° C, more preferably in the range of 80 to 130 ° C, and by appropriately controlling the polymerization temperature, 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 a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be performed in any of batch, semi-continuous and continuous methods. It can be carried out. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) 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. It is.

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

  The weight average molecular weight of the terminal unsaturated polypropylene produced in the step (A) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 60,000, and further preferably. Is in the range of 5,000 to 25,000. By being a terminal unsaturated polypropylene having a weight average molecular weight within the above range, in the step (C) described later, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin. The efficiency of introduction into the chain is increased. On the other hand, when exceeding the said range, the molar concentration of terminal unsaturated polypropylene will become relatively low, and the introduction | transduction efficiency to a principal chain will become low. Moreover, when it is less than the above range, there may be practical problems such as a decrease in melting point.

  The molecular weight distribution (Mw / Mn) of the terminal 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 terminally unsaturated polypropylenes having different molecular weights may be used.

The ratio of terminal unsaturation measured by ¹ H-NMR of the terminal unsaturated polypropylene produced in the step (A) is usually 0.1 to 6 per 1000 carbon atoms, more preferably 0.4 to 3.0. Furthermore, the proportion of terminal unsaturation having the terminal structure (I), the so-called amount of terminal vinyl, is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.2 to 2.0. It 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 (C) is low, and the amount of the graft polymer [R1] produced is small, so the desired effect cannot be obtained. There is a case.

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

[Process (B)]
Step (B) is a step of producing terminal unsaturated polyethylene as a raw material for the side chain (SE) composed of the ethylene polymer of the graft polymer [R1].

  In this step, ethylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [B] (hereinafter also referred to as complex [B]) of Group 4 or Group 5 of the periodic table having an organic ligand. And a process for producing terminally unsaturated polyethylene.

  The organic ligand may be a ligand having a cyclopentadienyl skeleton or a ligand not having a cyclopentadienyl skeleton, but efficiently generates terminal unsaturated polyethylene. From the viewpoint of making it, a phenoxyimine ligand is preferable.

  Here, the terminal unsaturated polyethylene includes polyethylene having a vinyl group at one end of the polymer chain, and the terminal unsaturated polyethylene is usually polyethylene having a vinyl group at one end, usually 60% by mass or more. , Preferably 70% by mass, more preferably 80% by mass or more, and still more preferably 90% by mass or more. In addition to polyethylene having a vinyl group at one end, polyethylene having an unsaturated carbon-carbon bond such as vinylene group or vinylidene group or saturated polyethylene at both ends may be included.

  The terminal vinyl ratio of the terminal unsaturated polyethylene (ratio of the number of vinyl groups to the total unsaturated carbon-carbon bonds) is usually 60% or more, preferably 70%, more preferably 80% or more, and even more preferably 90%. That's it.

The ratio of terminal vinyl groups in the terminal unsaturated polyethylene is usually 0.1 to 30 per 1000 carbon atoms, preferably in the range of 0.5 to 20, more preferably 1.0 to 10 Is in range. The content of the polyethylene having a vinyl group at one end and the ratio of the terminal vinyl group in the terminal unsaturated polyethylene can be calculated by a conventional method by molecular weight analysis by GPC measurement and polymer structure analysis by ¹ H-NMR measurement. .

  As described above, the transition metal compound of Group 4 or Group 5 having an organic ligand is preferably a Group 4 or Group 5 transition metal compound having a phenoxyimine ligand. Examples thereof include compounds disclosed in JP2003-073412 and JP2004-0776016.

More specifically, the complex [B] includes at least one transition metal compound selected from the following general formulas [B0], [B1], and [B2].
Complex [B] functions as a polymerization catalyst for producing terminal unsaturated polyethylene in combination with compound [D] described below.

（一般式［Ｂ０］中、Ｍは周期表第４〜５族の遷移金属原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、炭素原子数１〜２０の非環式炭化水素基（Ｃ_n'Ｈ_2n'+1、ｎ’＝１〜２０）または水素原子を示し、Ｒ²〜Ｒ⁶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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、また、Ｘで示される複数の基は互いに結合して環を形成してもよい。）

(In General Formula [B0], M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ represents an acyclic hydrocarbon having 1 to 20 carbon atoms. A group (C _{n ′} H _{2n ′ + 1} , n ′ = 1 to 20) or a hydrogen atom, R ^{2 to} R ⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, A heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of these being They may be connected to each other to form a ring, and when m is 2 or more, ^two groups represented by R ^{2 to} R ⁶ may be connected, and n is M Where X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. A boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, they are the same as each other Or may be different, and a plurality of groups represented by X may be bonded to each other to form a ring.)

（一般式［Ｂ１］中、Ｍは周期表第４〜５族の遷移金属原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、１つまたは複数の置換基を有していてもよい３〜１０員環の脂環式炭化水素基を示し、Ｒ²〜Ｒ⁶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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、また、Ｘで示される複数の基は互いに結合して環を形成してもよい。）

(In the general formula [B1], M represents a transition metal atom of Groups 4 to 5 in the periodic table, m represents an integer of 1 to 4, and R ¹ has one or more substituents. A alicyclic hydrocarbon group having 3 to 10 membered ring, wherein R ^{2 to} R ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, Indicates an oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these are connected to each other to form a ring Or when m is 2 or more, ^two groups represented by R ^{2 to} R ⁶ may be linked, and n is a number satisfying the valence of M. X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group Represents a group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. Or a plurality of groups represented by X may be bonded to each other to form a ring.)

（一般式［Ｂ２］中、Ｍは周期表第４〜５族の遷移金属原子を示し、ｍは１〜４の整数を示し、Ｒ¹は、１つまたは複数の置換基を有していてもよい炭素原子数４〜２０の少なくとも１つ以上の炭素を共有する２環性脂肪族炭化水素基であり、Ｒ²〜Ｒ⁶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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、また、ｍが２以上の場合にはＲ²〜Ｒ⁶で示される基のうち２個の基が連結されていてもよく、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合には、互いに同一であっても、異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）

(In general formula [B2], M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ has one or more substituents. Or a bicyclic aliphatic hydrocarbon group having at least one carbon atom having 4 to 20 carbon atoms, and R ^{2 to} R ⁶ may be the same or different from each other, and may be a hydrogen atom or a halogen atom. , Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, May be linked to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{2 to} R ⁶ may be linked. , N is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, An element-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; When n is 2 or more, they may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

  Hereinafter, characteristics of the chemical structure of the transition metal compound (B) used in the present invention will be described. The transition metal compound (B) is preferably at least one transition metal compound selected from the general formulas [B0], [B1], and [B2].

In the general formula [B0], R ¹ represents an acyclic hydrocarbon group having 1 to 20 carbon atoms (C _{n ′} H _{2n ′ + 1} , n ′ = 1 to 20) or a hydrogen atom. Preferably, it is a straight-chain hydrocarbon group having 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and the like. Can be mentioned. In these, a methyl group, an ethyl group, and n-propyl group are preferable. In the general formula [B0], R ¹ is more preferably a methyl group, an ethyl group, or a hydrogen atom.

In the general formula [B1], R ¹ represents a 3- to 10-membered alicyclic hydrocarbon group which may have one or more substituents. Specific examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the general formula [B1], the substituent that R ¹ may have is not particularly limited, but a halogen atom, hydrocarbon group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, oxygen-containing group, sulfur And a hydrocarbon group or a hydrocarbon-substituted silyl group which is a group selected from a containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group or a heterocyclic compound residue.

In the general formula [B1], as the substituent that R ¹ may have, specifically, a methyl group, an ethyl group, a propyl group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, a phenoxymethyl group, Examples include ethoxyethyl group, dimethylaminomethyl group, dimethylaminoethyl group, nitromethyl group, nitroethyl group, cyanomethyl group, cyanoethyl group, trimethylsilyl group, triethylsilyl group, and the like.

In the general formula [B1], when R ¹ is a 3- to 5-membered alicyclic hydrocarbon group having two or more substituents, the positions of the two or more substituents are not particularly limited.
In the general formula [B2], R ¹ is a bicyclic aliphatic hydrocarbon group having at least one carbon atom having 4 to 20 carbon atoms which may have one or more substituents. is there. Specific examples of the bicyclic aliphatic hydrocarbon group include spiro [2.2] pentane, spiro [2.3] hexane, spiro [2.4] heptane, spiro [2.5] octane, and spiro [3. 3] heptane, spiro [3.4] octane, spiro [3.5] nonane, spiro [4.4] nonane, spiro [4.5] decane, spiro [5.5] undecane, bicyclo [1.1. 0] butane, bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [3.1.0] hexane, bicyclo [3.2.0] heptane, bicyclo [3.3. 0] octane, bicyclo [4.1.0] heptane, bicyclo [4.2.0] octane, bicyclo [4.3.0] nonane, bicyclo [4.4.0] decane, bicyclo [1.1. 1] Pentane, bicyclo [2.1.1] Sun, bicyclo [2.2.1] heptane, bicyclo [2.2.2. ] Octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane, bicyclo [3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2]. Decane, bicyclo [3.3.3] undecane, and the like.

In the general formula [B2], R ¹ is preferably a bicyclic aliphatic hydrocarbon group sharing two carbons having 4 to 20 carbon atoms, which may have one or more substituents. Specific examples of the bicyclic aliphatic hydrocarbon group include bicyclo [1.1.0] butane, bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, and bicyclo [3.1. 0.0] hexane, bicyclo [3.2.0] heptane, bicyclo [3.3.0] octane, bicyclo [4.1.0] heptane, bicyclo [4.2.0] octane, bicyclo [4.3. .0] nonane, bicyclo [4.4.0] decane, bicyclo [1.1.1] pentane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2. .2. ] Octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane, bicyclo [3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2]. Decane, bicyclo [3.3.3] undecane, and the like.

In the general formula [B2], R ¹ is more preferably a bridged bicyclic aliphatic hydrocarbon sharing two carbon atoms of 5 to 20 carbon atoms, which may have one or more substituents. Specific examples of the bicyclic aliphatic hydrocarbon group include bicyclo [1.1.1] pentane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, and bicyclo [ 2.2.2. ] Octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane, bicyclo [3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2]. Decane, bicyclo [3.3.3] undecane, and the like.

In the general formula [B2], R ¹ is particularly preferably bicyclo [2.2.1] heptane which may have one or more substituents. In the general formula [B2], the substituent which R ¹ may have is not particularly limited, but a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, sulfur And a hydrocarbon group or a hydrocarbon-substituted silyl group which is a group selected from a containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group or a heterocyclic compound residue.

In the general formula [B2], specific examples of the substituent that R ¹ may have include a methyl group, an ethyl group, a propyl group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, and a phenoxymethyl group. Ethoxyethyl group, dimethylaminomethyl group, dimethylaminoethyl group, nitromethyl group, nitroethyl group, cyanomethyl group, cyanoethyl group, trimethylsilyl group, triethylsilyl group, and the like.

In the general formula [B2], the position of the two or more substituents is not particularly limited in the bicyclic hydrocarbon group having two or more R ¹ substituents.
In the general formulas [B0], [B1], and [B2], N ... M generally indicates coordination, but may or may not be coordinated in the present invention. May be.

  In general formulas [B0], [B1], and [B2], M independently represents a transition metal atom of Groups 4 to 5 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, and the like. And preferably a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium and hafnium, more preferably zirconium.

In the general formulas [B0], [B1], and [B2], m independently represents an integer of 1 to 4, preferably 1 to 2, and particularly preferably 2.
In the general formulas [B0], [B1], and [B2], R ^{2 to} R ⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic compound residue. , An oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are linked to each other to form a ring And when m is 2 or more, two of the groups represented by R ^{2 to} R ⁶ may be linked, and the halogen atom may be fluorine, chlorine, bromine , Iodine.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. Straight chain or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; straight chain having 2 to 30 carbon atoms such as vinyl group, allyl group and isopropenyl group, preferably 2 to 20 carbon atoms A chain or branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl group, propargyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl A cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as an adamantyl group, a cyclopentadienyl group, an indenyl group, Cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as oleenyl group; 6 to 30 carbon atoms such as phenyl group, benzyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group and anthracenyl group, preferably Includes 6 to 20 aryl groups; alkyl-substituted aryl groups such as tolyl group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group and di-t-butylphenyl group.

  In the hydrocarbon group, a hydrogen atom may be substituted with a halogen atom. For example, a halogenated carbon atom having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. A hydrogen group is mentioned. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Among these, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20 linear or branched alkyl groups; 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably 6 An aryl group having ˜20; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or aryloxy A substituted aryl group substituted with 1 to 5 substituents such as a group is preferred.

  Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group are the same as those exemplified above. Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

  Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, such as methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, and triethylsilyl groups. , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group and the like are preferable. In particular, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.
Next, the examples of R ^{2 to} R ⁶ described above will be described more specifically. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.

  Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.

  Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.

  Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetimide group and a benzimide group.

Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group. Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.

Specific examples of the sulfonamido group include a phenylsulfonamido group, an N-methylsulfonamido group, and an N-methyl-p-toluenesulfonamido group.
In the general formulas [B0] and [B1], R ⁶ is a branch having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc. A phenyl alkyl group, more preferably a phenylethyl group, a diphenylmethyl group, a cumyl group, a diphenylethyl group, a triphenylmethyl group, which is a group obtained by substituting a hydrogen atom of these groups with an aryl group having 6 to 20 carbon atoms, Further, it is preferably a group selected from cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., or phenyl, naphthyl, fluorenyl, anthranyl , 6 to 30 carbon atoms, such as phenanthryl, preferably 20 aryl group is also preferred, or a hydrocarbon-substituted silyl group.

R ^{2 to} R ⁶ are each a hydrocarbon ring containing two or more groups, preferably two or more groups adjacent to each other connected to each other to form an alicyclic ring, an aromatic ring, or a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, ^two groups out of the groups represented by R ^{2 to} R ⁶ may be linked. Further, when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other.

n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably an integer of 1 to 3.
In the general formulas [B0], [B1], and [B2], X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, or an aluminum-containing group. , A phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include the same groups as those exemplified above for R ^{2 to} R ⁶ . Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group, and eicosyl group; carbon such as cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group A cycloalkyl group having 3 to 30 atoms; an alkenyl group such as a vinyl group, a propenyl group and a cyclohexenyl group; an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group; a phenyl group, a tolyl group and a dimethylphenyl group , Aryl groups such as trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, and the like, but are not limited thereto. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.

Of these, those having 1 to 20 carbon atoms are preferred.
Examples of the heterocyclic compound residue include the same as those exemplified for R ^{2 to} R ⁶ .

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{2 to} R ^6. Specifically, the oxygen group includes a hydroxy group; Aryloxy groups such as methylphenoxy group, dimethylphenoxy group and naphthoxy group; arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; acetoxy group; carbonyl group and the like, but not limited thereto.

Examples of the sulfur-containing group are the same as those exemplified for R ^{2 to} R ⁶ , and specifically, methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group, benzyl sulfonate group, and the like. Sulfonate groups such as phonate group, p-toluene sulfonate group, trimethylbenzene sulfonate group, triisobutylbenzene sulfonate group, p-chlorobenzene sulfonate group, pentafluorobenzene sulfonate group; Sulfinate groups such as ruffinate groups, phenylsulfinate groups, benzylsulfinate groups, p-toluenesulfinate groups, trimethylbenzenesulfinate groups, pentafluorobenzenesulfinate groups; alkylthio groups; arylthio groups, etc. But only Not intended to be.

Specific examples of the nitrogen-containing group include the same groups as those exemplified above for R ^{2 to} R ^6. Specific examples include an amino group; a methylamino group, a dimethylamino group, a diethylamino group, and a dipropylamino group. Alkylamino groups such as dibutylamino group and dicyclohexylamino group; arylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group; It is not limited to these.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tolylphosphine group; methylphosphite group, ethyl Examples thereof include, but are not limited to, phosphite groups (phosphide groups) such as phosphite groups and phenyl phosphite groups; phosphonic acid groups; phosphinic acid groups.

Specific examples of the silicon-containing group include the same groups as those exemplified above for R ^{2 to} R ⁶ , and specifically, phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group. Group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group and other hydrocarbon-substituted silyl groups; trimethylsilyl ether group and other hydrocarbon-substituted silyl ether groups; trimethylsilylmethyl group and the like And silicon-substituted aryl groups such as trimethylsilylphenyl group.

Specific examples of the germanium-containing group include the same groups as those exemplified for R ^{2 to} R ⁶ , and specific examples include a group in which silicon in the silicon-containing group is replaced with germanium. Specific examples of the tin-containing group include the same groups as those exemplified above for R ^{2 to} R ⁶ , and more specifically, a group in which silicon of the silicon-containing group is substituted with tin.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO _4. Absent. Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (wherein R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.
Examples of preferred compound structures of the transition metal compounds represented by the above general formulas [B0], [B1], and [B2] include transition metal compounds disclosed in JP-A-2003-73412.
As described above, at least one transition metal compound selected from the general formulas [B0], [B1], and [B2] can be used alone or in combination of two or more.

[Preferred embodiment of transition metal compound (B)]
As the transition metal compound (B), at least one transition metal compound selected from the general formulas [B0], [B1], and [B2] is preferable, and a transition metal compound represented by the general formula [B0] is more preferable. The preferred embodiment of the transition metal compound represented by the general formula [B0] is as described above, and the particularly preferred embodiment is as follows.

In general formula [B0], M represents a transition metal atom of Group 4 of the periodic table,
m represents an integer of 1 to 4,
R ¹ is a linear hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
R ⁶ is a branched alkyl group having 3 to 20 carbon atoms, wherein at least one hydrogen atom is substituted with an aryl group having 6 to 20 carbon atoms,
n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, A halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is an integer of 2 or more, a plurality of Xs may be the same or different And a plurality of groups represented by X may be bonded to each other to form a ring.

[Process (C)]
The step (C) is produced in the step (B) with a terminal unsaturated polypropylene produced in the step (A) in the presence of an olefin polymerization catalyst containing a transition metal compound [C] belonging to Group 4 of the periodic table. A terminal unsaturated polyethylene, ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms.

  The olefin polymerization catalyst used in step (C) may be the same as or different from the olefin polymerization catalyst used in step (A). When it is the same as the olefin polymerization catalyst used in the step (A), it is preferable in that the catalyst used in the step (A) can be used also in the step (C).

In addition, the transition metal compound [C] of Group 4 of the periodic table is a superordinate concept of the transition metal compound [A] of Group 4 of the periodic table including a ligand having a dimethylsilylbisindenyl skeleton.
The transition metal compound [C] of Group 4 of the periodic table is preferably a Group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton. The cyclopentadienyl skeleton is recognized as a superordinate concept of the indenyl skeleton and the fluorenyl skeleton.

  When using a catalyst different from the olefin polymerization catalyst used in the step (A), the step (C) is preferably performed in the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound represented by the following general formula [C]. The terminal unsaturated polypropylene produced in the step (A), the terminal unsaturated polyethylene produced in the step (B), ethylene, and at least one α-olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms. This is a step of copolymerizing with olefin.

  The bridged metallocene compound represented by the following general formula [C] is also referred to as a bridged metallocene compound [C].

（式［Ｃ］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 [C], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. A hetero atom-containing group is shown, and two groups adjacent to each other among 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 heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, 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.
R ¹³ and R ¹⁴ each independently represents 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 nonconjugated diene having 4 to 10 carbon atoms, an anionic 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. )

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

From such a viewpoint, in order to obtain the olefin resin (β) containing a large amount of the graft polymer [R1], the bridged metallocene compound [C] is preferably used in the step (C).
The bridged metallocene compound [C] is combined with the compound [D] described later, the terminal unsaturated polypropylene produced in the step (A), the terminal unsaturated polyethylene produced in the step (B), ethylene, and carbon. It functions as an olefin polymerization catalyst that is copolymerized with at least one α-olefin selected from α-olefins having 3 to 20 atoms.

Hereinafter, characteristics of the chemical structure of the bridged metallocene compound [C] used in the present invention will be described.
The bridged metallocene compound [C] is structurally provided with the following features [m1] and [m2].

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

[M2] The two ligands are bonded by an aryl group-containing covalently bonded bridge portion (hereinafter also referred to as “bridge portion”) 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 bridge | crosslinking part, and other characteristics which bridge | crosslinking metallocene compound [C] has are demonstrated sequentially.

(Cyclopentadienyl group which may have a substituent)
In the formula [C], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. As a structure for taking in pyrene well, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R ¹ , R ² , R ³ and R ⁴ are methyl groups A structure in which the remainder is a hydrogen atom is particularly preferable.

(Substituted fluorenyl group)
In the formula [C], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. Or a silicon-containing group is preferable.

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 heteroatom-containing group other than a silicon-containing group, and the hydrogen atom, the hydrocarbon group and the silicon-containing group are preferable.

R ⁷ and R ¹⁰ are 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 the hydrogen atom, the hydrocarbon group and the silicon-containing group are preferable.

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.
However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, R ⁶ and R ¹¹ are preferably not hydrogen atoms, more preferably R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms, and R ⁶ and R ¹¹ are not preferred. Are 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 an aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic ring or an aromatic ring.
Illustrative and preferred groups for R ^{5 to} R ¹² include, for example, a hydrocarbon group (hereinafter sometimes referred to as “hydrocarbon group (f1)”) (preferably a hydrocarbon group having 1 to 20 carbon atoms). Alternatively, a silicon-containing group (hereinafter sometimes referred to as “silicon-containing group (f2)”) (preferably a silicon-containing group having 1 to 20 carbon atoms) may be mentioned.

  In addition, examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding silicon-containing groups (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups.

  Specific examples of the hydrocarbon group (f1) include 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, 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; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamanty group A cyclic saturated hydrocarbon group such as a group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group, and a nuclear alkyl substituent thereof; a saturated hydrocarbon such as a benzyl group and a cumyl group And a group in which at least one hydrogen atom of the group is substituted with an aryl group.

  The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms, such as a group in which a silicon atom is directly covalently bonded to the ring carbon of the cyclopentadienyl group. Specifically, an alkylsilyl group (eg, trimethylsilyl group) and an arylsilyl group (eg, triphenylsilyl group) can be mentioned.

  Specific examples of hetero atom-containing groups (excluding silicon-containing groups) include methoxy, ethoxy, phenoxy, N-methylamino, trifluoromethyl, tribromomethyl, pentafluoroethyl, and penta A fluorophenyl group is mentioned.

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

Examples of 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 an aromatic ring include compounds represented by general formulas [II] to [VI] described later. The group derived from it is mentioned as a suitable example.

(Bridged part)
In the formula [C], R ¹³ and R ¹⁴ each independently represents an aryl group, and Y ¹ represents a carbon atom or a silicon atom. The important point in the method for producing an olefin polymer is that the bridging atom Y ¹ of the bridging portion has R ¹³ and R ¹⁴ which are aryl groups which may be the same or different from each other. From the viewpoint of ease of production, it is preferable that R ¹³ and R ¹⁴ are the same.

  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 (sp2-type hydrogen) contained in the aryl group 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 a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a tolyl group, an isopropylphenyl group, and n-butylphenyl. Group, alkyl group-substituted aryl group such as t-butylphenyl group, dimethylphenyl group; cycloalkyl group-substituted aryl 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 (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group; The position of the substituent is preferably a meta position and / or a para position. Among these, a substituted phenyl group in which the substituent is located at the meta position and / or the para position is more preferable.

(Other features of bridged metallocene compounds)
In the formula [C], Q can be coordinated by a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a lone electron pair. 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 hydrocarbon group for Q is substituted with a halogen atom.
In the formula [C], M ¹ represents a zirconium atom or a hafnium atom, which is preferable in that the hafnium atom copolymerizes terminal unsaturated polypropylene with high efficiency and can be controlled to have a high molecular weight. The use of a catalyst having a performance capable of copolymerizing terminally unsaturated polypropylene with high efficiency and controllable to a high molecular weight is important for ensuring high productivity. This is because it is desirable to carry out the reaction under high temperature conditions in order to ensure high productivity, but the molecular weight produced tends to decrease under high temperature conditions.

(Example of preferred bridged metallocene compound [C])
Specific examples of the bridged metallocene compound [C] are shown below. 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 the formula [III]. And dibenzofluorenyl means a group derived from a compound having the structure represented by the formula [IV], and 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 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].

Examples of the bridged metallocene compound [C] include:
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) hafniu 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- (dimethyl Phenyl) -3,6-ditert-butylfluorenyl) ha Niumujikurorido, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert- 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-dihydro Cyclopentafluorenyl) 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 (cyclopentadi) Enyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6 -Di-tert-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-butylfur Olenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclo Pentadienyl) (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 (cyclo Pentadienyl) (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-butylfur Olenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclo Pentadienyl) (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 (cyclo Pentadienyl) (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 (cyclopentadi) Enil) (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-tetratert-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 dichlorine 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-tetra-tert-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 dichlorine 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-tetra-tert-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) Ru-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopenta Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3,3) 6,7-tetra-tert-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) methyle (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 (cyclo Pentadienyl) (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- ( Limethylphenyl) -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'-hexa Til-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-tetra-tert-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, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) 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 (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-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, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) 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 (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-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) hafniu 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- (dimethyl) Phenyl) -3,6-ditert-butylfluorenyl) ha Niumujikurorido, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butylfluorenyl) include hafnium dichloride.

  As the bridged metallocene compound [C], a compound in which “dichloride” in the above exemplified compounds is replaced with “difluoride”, “dibromide”, “diaiodide”, “dimethyl”, “methylethyl” or the like, “cyclopentadienyl” To “3-tert-butyl-5-methyl-cyclopentadienyl”, “3,5-dimethyl-cyclopentadienyl”, “3-tert-butyl-cyclopentadienyl” or “3-methyl-cyclo A compound 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. Examples of known methods include the methods described in WO 01/27124 and WO 04/029062 by the applicant.

The above bridged metallocene compound [C] is used singly or in combination of two or more.
The step (C) 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 polymer is used, but it has a step of obtaining the following polymerization reaction solution. Is preferred.

The step of obtaining a polymerization reaction liquid is preferably a bridged metallocene compound [C], more preferably R ¹³ or R ¹³ bonded to Y ¹ in the general formula [C] using an aliphatic hydrocarbon as a polymerization solvent. ¹⁴ is a phenyl group or a phenyl group substituted by an alkyl group or a halogen group, and R ⁷ and R ¹⁰ are ethylene in the presence of an olefin catalyst containing a bridged metallocene compound [C] having an alkyl substituent; The process of obtaining the polymerization reaction liquid of the copolymer of the C3-C20 alpha olefin, the terminal unsaturated polypropylene manufactured at a process (A), and the terminal unsaturated polyethylene manufactured at a process (B). It is.

  In step (C), the terminal unsaturated polypropylene produced in step (A) and the terminal unsaturated polyethylene produced in step (B) are fed to the reactor in step (C) in the form of a solution or slurry. Is done. The feed method is not particularly limited, and even if the polymerization liquid obtained in step (A) is continuously fed to the reactor in step (C), the steps (A) and (B) After the polymerization liquid is once stored in the buffer tank, it may be fed to the step (C).

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

  Moreover, it is preferable that the polymerization temperature of a process (C) is 90 degreeC or more, the range of 90-200 degreeC is more preferable, and it is especially preferable that it is the range of 100-200 degreeC. Such a temperature is preferable because the temperature at which the terminal unsaturated polypropylene is satisfactorily dissolved in aliphatic hydrocarbons such as hexane and heptane, which are preferably used industrially as the polymerization solvent, is 90 ° C. or higher. is there. A higher temperature is preferable for improving the amount of polypropylene side chain introduced. Furthermore, it is preferable that it is higher temperature also from a viewpoint of productivity improvement.

  The polymerization pressure in the step (C) is usually a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction may be performed in any of batch, semi-continuous and continuous methods. It can be carried out. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time of step (C) (average residence time when copolymerization is carried out in a continuous process) 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 (C), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoints of viscosity limitation in polymerization ability, post-treatment process (desolvation) load, and productivity, the content is preferably 15 to 35 wt%.

  The molecular weight of the resulting copolymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the usage-amount of compound [D] mentioned later. Specific examples of the compound [D] used for adjusting the molecular weight include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

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

  Compound [D] reacts with transition metal compound [A], complex [B] and bridged metallocene compound [C] to function as a catalyst for olefin polymerization. Specifically, [D1] organic metal The compound, [D2] an organoaluminum oxy compound, and [D3] a compound that reacts with the transition metal compound [A], the complex [B] or the bridged metallocene compound [C] to form an ion pair. . Hereinafter, the compounds [D1] to [D3] will be sequentially described.

([D1] organometallic compound)
Specific examples of the [D1] organometallic compound used in the present invention include an organoaluminum compound represented by the following general formula (D1-a), a periodic table Group 1 metal represented by the general formula (D1-b), and Examples thereof include complex alkylated products with aluminum, and dialkyl compounds of Group 2 or Group 12 metals represented by the general formula (D1-c). The [D1] organometallic compound does not include the [D2] organoaluminum oxy compound described later.

上記一般式（Ｄ１−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 (D1-a), R ^a and R ^b may be the same as or different from each other, and each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and p + q + r + s = 3. )

上記一般式（Ｄ１−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 general formula (D1-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（Ｄ１−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 (D1-c), R ^d and R ^e may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ represents Mg. Zn or Cd.

  Examples of the organoaluminum compound represented by the general formula (D1-a) include compounds represented by the following general formulas (D-1a-1) to (D-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０＜ｐ≦３、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、

(Wherein R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is 0 <p ≦ 3, preferably 1.5 ≦ p ≦ 3.) An organoaluminum compound represented by

（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はハロゲン原子を示し、ｐは０＜ｐ≦３、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, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is 0 <p ≦ 3, preferably 0 <p <3. An organoaluminum compound represented by:

（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０＜ｐ≦３、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, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is a number of 0 <p ≦ 3, preferably 2 ≦ p <3). Organoaluminum compounds,

（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 from each other, 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 a number of 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as an organoaluminum compound belonging to the general formula (D1-a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum 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;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b may be the same or different from each other and have a carbon atom number of 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (D1-a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (D1-b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (D1-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 [D1] organometallic compound, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, Butyl magnesium bromide, butyl magnesium chloride and the like can also be used.

In addition, 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 [D1] organometallic compound. You can also
[D1] Organometallic compounds as described above are used singly or in combination of two or more.

([D2] Organoaluminum oxy compound)
[D2] The organoaluminum oxy compound [D2] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. Good. [D2] Specific examples of the organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally 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, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.

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

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

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (D1-a).

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

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, 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 dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, it is preferably insoluble or hardly soluble in benzene.

  Examples of the [D2] organoaluminum oxy compound used in the present invention include an organoaluminum oxy compound containing boron 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 s} may be the same as or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number. 1 to 10 hydrocarbon groups are shown.)

  The organoaluminum oxy compound containing boron represented by the general formula (III) includes an alkyl boronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. In particular, it can be produced by reacting at a temperature of −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 general formula (IV), R ¹⁹ represents the same group as R ¹⁷ in general formula (III).)

  Specific examples of the alkyl boronic acid represented by the general formula (IV) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic 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 (D1-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.
[D2] Organoaluminum oxy compounds as described above are used singly or in combination of two or more.

  ([D3] transition metal compound [A], complex [B] or bridged metallocene compound [C] reacts to form an ion pair) Transition metal compound [A], complex [B] used in the present invention Or as compound [D3] (henceforth "ionized ionic compound") which reacts with bridge | crosslinking metallocene compound [C] and forms an ion pair, Unexamined-Japanese-Patent No. 1-501950, Unexamined-Japanese-Patent No. 1-502036 Lewis acids, ionic compounds, and boranes described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, and the like. Examples thereof include 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 or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.) is used. For example, 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 ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal, and R ^{21 to} R ^24. May be the same or different from each other and are organic groups, preferably aryl groups or substituted aryl groups.

  Specific examples of the carbonium cation 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 cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cation Etc.

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

R ²⁰ is preferably a carbonium cation or an ammonium cation, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

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

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and 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-ditrifluoromethyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  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, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

  Specific examples of the dialkylammonium 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 Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds 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.)

Specifically as a borane compound which is an example of an ionized ionic compound (compound [D3]), 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 Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds that are examples of ionized ionic compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3- Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-dicarbaound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) L) 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-carboundecaborate, tri (n-butyl) ammonium 7-carbundecaborate, tri (n-butyl) ammonium 7,8-dicarboundeborate, 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-dicarbaoundeca Rate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundedecaborate, Anions such as tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salt of;
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-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) 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-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound that is an example of the ionized ionic compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. 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, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, but not limited thereto. In addition, the salt includes, for example, a metal of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Examples thereof include organic salts such as salts and triphenylethyl salts.

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

  The above ionized ionic compounds (compounds that react with [D3] transition metal compound [A], complex [B] or bridged metallocene compound [C] to form an ion pair) are used singly or in combination. Used in combination.

  When [D2] organoaluminum oxy compounds such as methylaluminoxane as a co-catalyst component are used in combination with transition metal compound [A], complex [B], and bridged metallocene compound [C], it is very high for olefin compounds. Shows polymerization activity.

[D3] ionized ionic compounds as described above are used singly or in combination of two or more.
The organometallic compound [D1] has a molar ratio (D1 / M) of the organometallic compound [D1] to the transition metal atom (M) in the transition metal compound [A] in the step (A). ) Is a molar ratio (D1 / M) with the transition metal atom (M) in the complex [B], and in step (C) is a molar ratio with the transition metal atom (M) in the bridged metallocene compound [C]. (D1 / M) is usually used in an amount such that it is 0.01 to 100,000, preferably 0.05 to 50,000.

  The organoaluminum oxy compound [D2] is a molar ratio (D2 / M) of the aluminum atom in the organoaluminum oxy compound [D2] and the transition metal atom (M) in the transition metal compound [A] in the step (A). ) Is a molar ratio (D2 / M) with the transition metal atom (M) in the complex [B] in the step (B), and the transition metal atom (C) in the bridged metallocene compound [C] in the step (C). M) is used in such an amount that the molar ratio (D2 / M) is usually 10 to 500,000, preferably 20 to 100,000. .

  The ionized ionic compound [D3] has a molar ratio (D3 / M) between the ionized ionic compound [D3] and the transition metal atom (M) in the transition metal compound [A] in the step (A). In (B), the molar ratio (D3 / M) with the transition metal atom (M) in the complex [B] is different from the transition metal atom (M) in the transition metal compound [C] in the step (C). The molar ratio (D3 / M) is usually 1 to 10, preferably 1 to 5. .

[Process (D)]
In addition to the steps (A), (B) and (C), the method for producing the olefin resin (β) may include a step (D) for recovering the polymer produced in each step, if necessary. This step is a step of separating the organic solvent used in steps (A), (B) and (C), taking out the polymer and converting it to a product form, and existing polyolefins such as solvent concentration, extrusion degassing, pelletizing, etc. There is no particular limitation as long as it is a process for producing a resin.

[Composition]
The olefin resin (β) of the present invention is only the olefin resin (β) and may be used for various applications. However, other resins, rubbers, inorganic fillers, and additives are added as long as the object of the present invention is not impaired. It can be used as a composition containing an agent or the like.

  Additives include weather resistance stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant And crystal nucleating agents.

In the present invention, a composition containing at least a resin other than the olefin resin (β) and the olefin resin (β) is referred to as a resin composition.
Examples of the composition of the present invention include an embodiment in which the olefin resin (β) is contained in an amount of 1% by mass or more and less than 100% by mass in 100% by mass of the composition.

<Resin composition>
The olefin resin (β) of the present invention comprises a main chain (MC) composed of an ethylene / α-olefin copolymer, a side chain (SE) composed of an ethylene polymer, and a propylene polymer. Therefore, a resin composition having excellent characteristics and excellent compatibility with any of general propylene resins and ethylene resins can be obtained.

  Below, a propylene resin (α-1), which is a typical resin composition, and a propylene resin composition containing an olefin resin (β), an ethylene resin (α-2), and an olefin resin ( A resin composition containing an ethylene resin composition containing β), a propylene resin (α-1), an ethylene resin (α-2), and an olefin resin (β) will be described.

<Propylene-based resin composition>
The propylene resin composition of the present invention comprises a propylene resin (α-1) and the olefin resin (β).

  Since the above-mentioned olefin resin (β) is well compatible with the propylene resin (α-1) at an arbitrary blending ratio, the propylene resin (α-1) in the propylene resin composition of the present invention. ) And the content ratio of the olefin resin (β) is not particularly limited, but as a content ratio that improves impact resistance and toughness while maintaining good properties such as rigidity and hardness inherent to the propylene resin, The propylene-based resin (α-1) is usually 2 to 98 parts by mass, preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, and 65 to 95 parts by mass. Is more preferable. Moreover, olefin resin ((beta)) is 2-98 mass parts normally, It is preferable that it is 2-50 mass parts, It is more preferable that it is 5-40 mass parts, It is 5-35 mass parts. Is more preferable. However, the total of the propylene resin (α-1) and the olefin resin (β) is 100 parts by mass.

  When the content ratio of the propylene resin (α-1) and the olefin resin (β) is in the above range, the propylene resin composition of the present invention maintains excellent properties such as the original rigidity and hardness of the propylene resin. However, impact resistance and toughness are improved, and it can be suitably used for manufacturing various molded products.

Next, the propylene-based resin (α-1) will be described below.
The propylene-based resin (α-1) is different from the olefin-based resin (β), and is a homopolymer of propylene, or from propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms. It comprises a copolymer with at least one selected α-olefin. 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, 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, - decene, 1-undecene, 1-dodecene, and the like can be given. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.

  Propylene-type resin ((alpha) -1) may be comprised from the single polymer among the said polymers, and may be comprised from the some polymer. The propylene resin (α-1) is polymerized with a Ziegler-Natta catalyst or the like.

  The propylene resin (α-1) can be used without particular limitation from among commercially available propylene resins. Examples of commercially available propylene resins include so-called homopolypropylene resins, random polypropylene resins, and block polypropylene resins.

  Homopolypropylene resin is a resin composed essentially of a homopolymer of propylene, is inexpensive and easy to manufacture, is excellent in rigidity and surface hardness, but inferior in impact resistance and toughness. When the homopolypropylene resin is used as the propylene-based resin (α-1) in the propylene-based resin composition of the present invention, the olefin-based resin (β) retains excellent characteristics such as the rigidity of the homopolypropylene resin, Impact resistance and toughness can be significantly improved.

  The random polypropylene resin is a resin mainly composed of a propylene-based polymer containing a small amount of a comonomer, and has higher impact resistance and transparency than a homopolypropylene resin. When a random polypropylene resin is used as the propylene resin (α-1) in the propylene resin composition of the present invention, the olefin resin (β) maintains the rigidity of the random polypropylene resin, The toughness and surface hardness can be improved, and particularly the low temperature impact resistance can be greatly improved.

  As described in the background art, the block polypropylene resin is a two-stage polymerization composition of a propylene-based polymer and an ethylene-propylene copolymer, and the term “block” in the block polypropylene resin does not mean “block copolymer”. However, by including an ethylene propylene copolymer, the balance between rigidity and impact resistance of the block polypropylene resin is improved as compared with the homopolypropylene resin. When a block polypropylene resin is used in the propylene resin composition of the invention, the olefin resin (β) provides a high level of reciprocal physical properties such as rigidity and impact resistance to a level that cannot be achieved with a normal block polypropylene resin. The balance can be improved.

  Hereinafter, the preferable aspect of propylene-type resin ((alpha) -1) is demonstrated. The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the propylene-based resin (α-1) is usually 0.1 to 500 g / 10 minutes. The lower limit of MFR 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. is there. When the MFR of the propylene resin (α-1) is 0.1 g / 10 min or more, the dispersibility of the propylene resin (α-1) and the olefin resin (β) in the propylene resin composition is improved. It is favorable and preferable in terms of mechanical strength of the resin composition. Moreover, when MFR of propylene-type resin ((alpha) -1) is 500 g / 10min or less, it is preferable in the intensity | strength of propylene-type resin ((alpha) -1) itself, and the mechanical strength of a resin composition.

  MFR serves as an index of the molecular weight of the propylene-based resin (α-1), but the propylene-based resin (α-1) preferably further has a weight average molecular weight in terms of polypropylene determined by gel permeation chromatography (GPC). 80,000 to 900,000, more preferably 100,000 to 700,000, particularly preferably 150,000 to 700,000.

  Further, the propylene resin (α-1) preferably has a tensile 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 obtained by measuring a 2 mm-thick press sheet at 23 ° C. in accordance with JIS K7113-2. When the propylene polymer (α-1) has a tensile modulus in the above range, the propylene resin composition containing the propylene polymer (α-1) has high rigidity and high hardness.

<Ethylene resin composition>
The ethylene resin composition of the present invention is characterized by containing an ethylene resin (α-2) and the olefin resin (β).

  Since the above-mentioned olefin resin (β) is well compatible with the ethylene resin (α-2) at an arbitrary blending ratio, the ethylene resin (α-2) in the ethylene resin composition of the present invention is used. ) And the content ratio of the olefin resin (β) is not particularly limited, but the ethylene resin (α-2) is usually 2 to 98 parts by mass, preferably 50 to 98 parts by mass. 60 to 95 parts by mass, more preferably 65 to 95 parts by mass. The olefin resin (β) is usually 2 to 98 parts by mass, preferably 2 to 50 parts by mass, more preferably 5 to 40 parts by mass, and 5 to 35 parts by mass. More preferably. However, the total of the ethylene resin (α-2) and the olefin resin (β) is 100 parts by mass.

Next, the ethylene resin (α-2) will be described below.
The ethylene resin (α-2) is different from the olefin resin (β) and is a homopolymer of ethylene or selected from ethylene and an α-olefin having 3 to 20 carbon atoms. It is composed of a copolymer with at least one α-olefin. The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene and 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, - nonene, 1-decene, 1-undecene, 1-dodecene and the like. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.

  The ethylene resin (α-2) may be composed of a single polymer or a plurality of polymers among the polymers. The ethylene resin (α-2) is polymerized with a Ziegler-Natta catalyst or the like.

  As ethylene resin ((alpha) -2), it can use without a restriction | limiting especially from commercially available ethylene resin. Examples of commercially available ethylene resins include so-called high density polyethylene resins, linear low density polyethylene resins, and high pressure method low density polyethylene resins.

  A high-density polyethylene resin is a resin composed of an ethylene homopolymer or a copolymer of ethylene and a small amount of an α-olefin, is inexpensive and easy to produce, and has excellent rigidity and the like, but is inferior in impact resistance and toughness. When a high density polyethylene resin is used as the ethylene resin (α-2) in the ethylene resin composition of the present invention, the olefin resin (β) retains excellent characteristics such as rigidity of the high density polyethylene resin. However, impact resistance and toughness can be improved.

  The linear low density polyethylene resin is a resin composed of a copolymer containing ethylene as a main component and an α-olefin as a comonomer, and has higher impact resistance and transparency than a high density polyethylene resin. When a linear low density polyethylene resin is used as the polyethylene resin (α-2) in the ethylene resin composition of the present invention, toughness and surface hardness can be improved by the olefin resin (β).

  Hereinafter, the preferable aspect of ethylene-type resin ((alpha) -2) is demonstrated. The melt flow rate (MFR: ASTM D1238, 190 ° C., load 2.16 kg) of the ethylene-based resin (α-2) is usually 0.1 to 500 g / 10 minutes. The lower limit of MFR 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. is there. When the MFR of the ethylene resin (α-2) is 0.1 g / 10 min or more, the dispersibility of the ethylene resin (α-2) and the olefin resin (β) in the ethylene resin composition is good. Therefore, the mechanical strength of the resin composition is preferable. Further, the MFR of the ethylene resin (α-2) is preferably 500 g / 10 min or less from the viewpoint of the strength of the ethylene resin (α-2) itself and the mechanical strength of the resin composition.

<Resin Composition Containing Propylene Resin (α-1), Ethylene Resin (α-2), and Olefin Resin (β)>
The resin composition containing the propylene-based resin (α-1), ethylene-based resin (α-2), and olefin-based resin (β) of the present invention will be described below.

  As the propylene-based resin (α-1) contained in the resin composition, those exemplified in the section <Propylene-based resin composition> can be used. In addition, as the ethylene resin (α-2) contained in the resin composition, those exemplified in the section <Ethylene resin composition> can be used.

  The blending ratio of the olefin resin (β), propylene resin (α-1), and ethylene resin (α-2) contained in the composition is arbitrary, but the olefin resin (β) is usually used. 2 to 98 parts by mass, preferably 2 to 50 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 5 to 35 parts by mass, and a propylene resin (α-1) and an ethylene resin (α-2). ) In general, usually 2 to 98 parts by mass, preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, and even more preferably 65 to 95 parts by mass, and a propylene resin (α- The ratio of the content of 1) to the ethylene resin (α-2) is usually 1:99 to 99: 1, preferably 10:90 to 90:10. However, the total of the olefin resin (β), the propylene resin (α-1), and the ethylene resin (α-2) is 100 parts by mass.

<Other ingredients>
Resin composition of the present invention (for example, resin containing propylene resin composition, ethylene resin composition, propylene resin (α-1), ethylene resin (α-2), and olefin resin (β) The composition) can be blended with other resins, rubbers, inorganic fillers, organic fillers, etc. within the range not impairing the object of the present invention, and also can be weather resistant stabilizers, heat stabilizers, antistatic agents, Additives such as crystal nucleating agents such as anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants can be blended. The addition amount of the other resin, other rubber, inorganic filler, additive and the like is not particularly limited as long as the object of the present invention is not impaired.

<Method for producing resin composition>
The method for preparing the resin composition in the present invention is not particularly limited, such as a melting method or a solution method, but in practice, a melt-kneading method is preferable. As a melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are mixed uniformly with a Henschel mixer, a ribbon blender, a V-type blender, etc., together with the additives described in the additional component section if necessary, and then uniaxial or multiaxial kneading. It can be prepared by kneading with an extruder, kneading roll, batch kneader, kneader, Banbury mixer or the like.

  The melt kneading temperature of each component (for example, cylinder temperature in the case of an extruder) depends on the type of resin used, but 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 resin composition can improve impact resistance while maintaining rigidity, and has an excellent balance between rigidity and impact resistance. Therefore, injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, It can be molded into various molded products by known molding methods such as injection blow molding, press molding, vacuum molding, calendar molding, foam molding, etc., containers for automobile parts, food applications, medical applications, food applications and electronic materials. It can be applied to various known uses such as packaging materials for applications, films, sheets and tapes.

  Since the molded body made of the resin composition has an excellent balance between rigidity and impact resistance, has a high surface hardness, and is excellent in chemical resistance, it can be used for various automobile parts. For example, automotive exterior parts such as bumpers, side moldings and aerodynamic undercovers, automotive interior parts such as instrument panels and interior trims, outer panel parts such as fenders, door panels and steps, engine covers such as engine covers, fans and fan shrouds It can be used for parts.

  Examples of containers for food use and medical use include food containers such as tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, beverage bottles, retort containers, bottles Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottle chemical containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. .

  Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials, and freshness. Retaining film, pharmaceutical packaging material, cell culture bag, cell inspection film, bulb packaging material, seed packaging material, film for vegetable / mushroom cultivation, heat-resistant vacuum forming container, side dish container, side dish cover, commercial wrap film, home use Wrap film, baking carton, etc. are mentioned.

Films, sheets, and tapes include, for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical components, protective films for lenses, protective films for electrical components and electrical appliances, protective films for mobile phones, and PCs. Protective films such as protective films, masking films, condenser films, reflective films, laminates (including glass), radiation resistant films, gamma ray resistant films, porous films,
Other uses include, for example, housings for home appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, cosmetic / perfume spray tubes, medical tubes, infusion tubes, pipes, wire harnesses, motorcycles / railways Interior materials for vehicles, aircraft, ships, etc., instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, armrest, airbag case lid, shift knob, assist grip, side step Mat, reclining cover, trunk seat, seat belt buckle, inner / outer molding, roof molding, belt molding and other molding materials, door seals, body sealing and other automotive sealing materials, glass run channels, mudguards, Automotive interior and exterior materials such as a rocking plate, step mat, license plate housing, automotive hose member, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, bonnet cushion, door cushion, damping tire, Special tires such as static tires, car race tires, radio control tires, packing, automotive dust covers, lamp seals, automotive boot materials, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, furniture / Skin materials for footwear, clothing, bags, building materials, etc., sealing materials for construction, waterproof sheets, building material sheets, gaskets for building materials, window films for building materials, iron core protection members, gaskets, doors, door frames, window frames, peripheral edges Baseboard, open frame, flooring, ceiling material, wallpaper, health supplies (eg, non-slip mats / sheets, anti-tip films / mats / sheets), health appliances, shock absorbing pads, protectors / protectors (eg : Helmets, guards), sports equipment (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, transport equipment (eg transport shock absorbing grips, shock absorbing sheets), vibration control Pallet, shock absorbing damper, insulator, shock absorbing material for footwear, shock absorbing foam, shock absorbing material such as shock absorbing film, grip material, miscellaneous goods, toys, shoe sole, shoe sole, shoe midsole / inner sole, Sole, sandals, suction cups, toothbrushes, floor materials, gymnastic mats, power tool members, agricultural equipment members, heat dissipation materials, transparent substrates, soundproofing materials, food After filling the bottle with baby food / dairy products / pharmaceuticals / sterilized water, etc., it is subjected to high-temperature treatment such as boiling and high-pressure steam sterilization. Packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as plastic 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, OA heat-resistant packing, animal cages, beakers, measuring cylinders, laboratory instruments, optical measurement cells, costume cases, clear cases, clear files, clear sheets, desk mats, For use as a fiber, for example, non-woven fabric, non-stretchable Cloth, fiber, waterproof cloth, breathable fabric and cloth, disposable diapers, sanitary products, sanitary products, filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, etc. .

  Among these, the molded body obtained from the resin composition can improve impact resistance while maintaining rigidity, and has an excellent balance between rigidity and impact resistance. It can be suitably used for automobile interior and exterior materials, outer plate materials, food containers, and beverage containers.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
In the following examples, the physical properties of the olefin resin (β), (β ′), (β ″), the propylene resin (α-1), the ethylene resin (α-2), the resin composition, It measured by the following method.

(Olefin resins (β), (β ′), (β ″), physical properties of terminal unsaturated polypropylene and terminal unsaturated polyethylene)
(1) Measurement of melting point (Tm) The melting point (Tm) was measured by DSC measurement under the following conditions.
Using a differential scanning calorimeter [SII RDC220], a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then heated to 200 ° C. at a temperature raising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was defined as the melting peak, and the temperature at which the melting peak appears was determined as the melting point (Tm).

(2) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) was measured by DSC measurement under the following conditions.
Using a differential scanning calorimeter [SII DSC220], about 5.0 mg of the sample was heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere and held at that temperature for 10 minutes. Further, after cooling to −100 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The glass transition temperature (Tg) is sensed in such a manner that the DSC curve is bent due to the change in specific heat and the base line moves in parallel during the second temperature increase. The glass transition temperature (Tg) was defined as the temperature at the intersection of the tangent to the base line, which is lower than the bending, and the tangent at the point where the inclination is maximum at the bent portion.

(3) Measurement of ratio of propylene polymer contained in olefin resin (β), (β ″) to olefin resin (β), (β ″) As described above, terminal used in step (C) It calculated from the ratio of the weight of unsaturated polypropylene and the weight of the obtained olefin resin ((beta)) and ((beta '')).

(4) Measurement of ratio of ethylene polymer to olefin resin (β) contained in olefin resin (β) As described above, the weight of terminal unsaturated polyethylene used in step (C) and the obtained olefin It calculated from the ratio of the weight of the system resin (β).

(5) Adhesion test As an evaluation of the stickiness of the olefin resin (β), an adhesion test of the resin sheet was performed as follows. When the peel strength is high, the stickiness is large, and when the peel strength is low, it can be said that the resin has little stickiness. First, a press sheet sample having a thickness of 0.1 mm was prepared, and the two press sheet samples were overlapped and processed at 40 ° C. for 24 hours under a load of 500 kgf / m ² . A T-type peel test was performed at a measurement temperature of 23.0 ° C., a test speed of 200.0 mm / min, and a test piece width of 80.0 mm, and the adhesive strength was measured. In addition, when the adhesive strength was remarkably strong and the sample did not peel and the sample was stretched or the sample was broken at the chucking portion, it was evaluated as “no peel”.

(6) Tensile test Tensile modulus was measured according to ASTM D638.

(7) Intrinsic viscosity measurement The intrinsic viscosity measurement [η] was measured in decalin at 135 ° C.
Specifically, about 20 mg of resin was dissolved in 25 ml of decalin, and then the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner as described above.
This dilution operation was further repeated twice, 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) ¹³ C-NMR measurement Confirmation of composition ratio analysis of resin ethylene and α-olefin, and stereoregularity of terminal unsaturated polypropylene (isotactic pentad fraction (mmmm: [%])) For the purpose, ¹³ C-NMR measurement was performed under the following conditions.

Apparatus: AVANCE III500 CryoProbe Prodigy type nuclear magnetic resonance apparatus manufactured by Bruker Biospin Co., Ltd., 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, number of integrations: 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).

(9) ¹ H-NMR measurement For the analysis of the terminal structure of terminal unsaturated polypropylene and terminal unsaturated polyethylene, ¹ H-NMR measurement was performed under the following conditions.

Apparatus: ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL, Measurement nucleus: ¹ 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, integration number: 512 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).

(10) GPC measurement For the molecular weight analysis of the polymer, GPC analysis was performed under the following conditions.
Apparatus: Waters Alliance GPC 2000 type, column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm × 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 volume: 0.5 mL, sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).

  The average molecular weight in terms of polystyrene obtained by the above measurement is converted into polyethylene for the following olefin resins β′-1 to β′-4 and terminal unsaturated polyethylenes E-1 and E-2, and terminal unsaturated polypropylene. P-1 and P-2 were converted to polypropylene.

(Propylene-based resin (α-1), ethylene-based resin (α-2) and method for measuring physical properties of resin composition)
(11) Melt flow rate (MFR: [g / 10 min])
The melt flow rate was measured with a 2.16 kg load according to ASTM D1238E. The measurement temperature was 230 ° C. for propylene resin and 190 ° C. for ethylene resin.

(12) Melting point The melting point was measured by the same method as in (1) above.

(13) Isotactic pentad fraction (mmmm: [%])
One of the indexes of the stereoregularity of the polymer, the pentad fraction (mmmm,%) whose microtacticity was investigated was based on Macromolecules 8,687 (1975) in the propylene-based resin (α-1). It was calculated from the peak intensity ratio of the assigned ¹³ C-NMR spectrum. ^{The 13} C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, using a temperature of 130 ° C. and an o-dichlorobenzene solvent.

(14) Flexural modulus The flexural modulus (FM: [MPa]) was measured under the following conditions in accordance with JIS K7171.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm

(15) Charpy impact test The Charpy impact test ([kJ / m ² ]) was performed according to JIS K7111, under the following conditions.
<Test conditions>
Temperature: -30 ° C, 0 ° C, 23 ° C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
Notch is machined

(16) Tensile elongation at break The tensile test was performed according to JIS K7202 under the following conditions.
<Measurement conditions>
Test piece: JIS K7162-BA dumbbell
5mm (width) x 2mm (thickness) x 75mm (length)
Tensile speed: 20 mm / min Distance between spans: 58 mm

(17) Rockwell hardness The Rockwell hardness (R scale) was measured according to JIS K7202 under the following conditions.
<Measurement conditions>
Test piece: width 30 mm, length 30 mm, thickness 2 mm
Measured by stacking two test pieces

(18) High-speed surface impact test The high-speed surface impact test was performed under the following conditions.
<Measurement conditions>
Test piece: Square plate 30 mm (width) x 30 mm (length) x 2 mm (thickness)
Striker diameter: 1/2 inch Support base diameter: 1 inch Test temperature: 0 ° C
Hereinafter, the Example and comparative example of an olefin resin ((beta)) are described. In some cases, manufacturing is performed multiple times to secure the amount of analysis.

[Example 1]
Step (A): Production of Terminally Unsaturated Polypropylene (P-1) Dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride used as a catalyst (transition metal compound [A]) is disclosed in Japanese Patent No. 3737134. Synthesized according to the disclosed method.

  To a 1 L stainless steel autoclave sufficiently purged with nitrogen, 500 mL of toluene and 0.67 mL (1.0 mmol) of a toluene solution (1.5 mol / L) of methylaluminoxane (also referred to as PMAO) were placed under a nitrogen flow. Thereafter, the autoclave was closed and the temperature was raised to 85 ° C. Next, the propylene partial pressure was increased to 0.3 MPa while stirring the interior of the polymerization vessel at 600 rpm, and then maintained at 85 ° C. Therein, 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol / L) of dimethylsilylbis (2-methyl-4-finylindenyl) zirconium dichloride was injected to initiate polymerization. The pressure was maintained while continuously supplying propylene gas, and the polymerization was carried out at 85 ° C. for 20 minutes, and then the polymerization was stopped by injecting 5 mL of methanol.

  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 14.9 g of terminal unsaturated polypropylene (P-1). The analysis results of the obtained polymer are shown in Table 1.

Step (B): Production of Terminal Unsaturated Polyethylene (E-1) Compound (1) used as a catalyst was synthesized according to [Synthesis Example 3] of International Patent Publication WO2006 / 057229, and a macromonomer (terminal unsaturated polyethylene). (E-1)) was synthesized according to the same publication [Example 1].

The product (terminal unsaturated polyethylene (E-1)) had Mw = 1550, Mw / Mn = 2.32 in terms of polyethylene, and ^one -terminal unsaturated ratio measured by ¹ H-NMR = 99.0 mol%. The analysis results are also shown in Table 2.

Step (C): Production of Olefin Resin (β-1) Compound (2) represented by the following formula used as a catalyst was synthesized by a known method.
A glass reactor having an internal volume of 1 L, which was sufficiently purged with nitrogen, was charged with 10.0 g of terminal unsaturated polypropylene (P-1), 5.0 g of terminal unsaturated polyethylene (E-1) and 500 ml of xylene. The temperature was raised to 0 ° C. to dissolve the macromonomers (P-1 and E-1).

Then, 120 liter / hr of ethylene and 15 liter / hr of 1-butene were continuously supplied to saturate the liquid phase and the gas phase. Subsequently, 1.0 mL (1.0 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al) in a state where ethylene and 1-butene were continuously supplied, the compound (2) Of toluene solution (0.0020 mol / L) of 5.0 mL (0.010 mmol), followed by toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) (4.0 mmol / L) was added at 6.3 mL (0.025 mmol), and polymerization was carried out at 97 ° C. for 40 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol.

  The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 41.9 g of an olefin resin (β-1). Table 3 shows the analysis results of the olefin resin (β-1).

  A resin (β′-1) obtained by polymerization in the same manner as in Example 1 except that the terminal unsaturated polypropylene (P-1) and the terminal unsaturated polyethylene (E-1) are not added in Comparative Example 1 described later. Table 4 shows the results of analysis performed by the method described above. This resin (β′-1) was assumed to be a copolymer constituting the main chain of the olefin resin (β-1).

[Example 2]
Step (A): Production of terminal unsaturated polypropylene (P-2) 1.5 L of toluene was placed in a 2 L glass reactor sufficiently purged with nitrogen, and then heated 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. Subsequently, in a state where propylene was continuously supplied, 5.0 mL (7.5 mmol) of a toluene solution (1.5 mol / L) of methylaluminoxane (also referred to as DMAO) and then dimethylsilylbis (2-methyl-4-fini) were added. 6.0 mL (0.012 mmol) of a toluene solution (0.0020 mol / L) of ruindenyl) zirconium dichloride was added, and polymerization was performed at 85 ° C. for 30 minutes under normal pressure. The polymerization was stopped 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 (P-2)). The analysis results of the obtained polymer are shown in Table 1.

Step (C): Production of Olefin Resin (β-2) Except that the step (C) was carried out using the terminal unsaturated polypropylene (P-2) instead of the terminal unsaturated polypropylene (P-1). An olefin resin was produced in the same manner as in Example 1. 40.2g of olefin resin ((beta) -2) was obtained. Table 3 shows the analysis results of the olefin resin (β-2).

[Example 3]
Step (C): Production of Olefin Resin (β-3) Olefin as in Example 2 except that Step (C) was carried out with 1.0 g of terminal unsaturated polyethylene (E-1) charged. Based resin was produced. 37.0g of olefin resin ((beta) -3) was obtained. Table 3 shows the analysis results of the olefin resin (β-3).

[Example 4]
Step (C): Production of Olefin Resin (β-4) Olefin as in Example 3 except that Step (C) was carried out with 5.0 g of terminal unsaturated polypropylene (P-2) charged. Based resin was produced. 33.2g of olefin resin ((beta) -4) was obtained. Table 3 shows the analysis results of the olefin resin (β-4).

[Example 5]
Step (C): Production of Olefin Resin (β-5) Olefin as in Example 2 except that Step (C) was carried out with the amount of terminal unsaturated polypropylene (P-2) charged to 2.5 g. Based resin was produced. 33.8g of olefin resin ((beta) -5) was obtained. Table 3 shows the analysis results of the olefin resin (β-5).

[Example 6]
Step (C): Production of Olefin Resin (β-6) Olefin as in Example 2 except that Step (C) was carried out with 5.0 g of terminal unsaturated polypropylene (P-2) being charged. Based resin was produced. 36.8g of olefin resin ((beta) -6) was obtained. Table 3 shows the analysis results of the olefin resin (β-6).

[Example 7]
Step (B): Production of Terminal Unsaturated Polyethylene (E-2) Compound (3) and macromonomer (terminal unsaturated polyethylene (E-2)) used as a catalyst are disclosed in [Synthesis Example 2] of JP2013-220992. ] And synthesized. The product had Mw = 4770, Mw / Mn = 2.25, and single-terminal unsaturation as measured by ¹ H-NMR = 97.0 mol% in terms of polyethylene. In the following compound (3), Et represents an ethyl group. The analysis results are also shown in Table 2.

Process (C): Manufacture of olefin resin (β-7) Except that terminal unsaturated polyethylene (E-2) was used instead of terminal unsaturated polyethylene (E-1), and the process (C) was carried out. An olefin resin was produced in the same manner as in Example 6. 32.6 g of olefin resin (β-7) was obtained. Table 3 shows the analysis results of the olefin resin (β-7).

[Example 8]
Step (C): Production of Olefin Resin (β-8) Into a glass reactor having an internal volume of 1 L sufficiently purged with nitrogen, 5.0 g of terminal unsaturated polypropylene (P-2) and terminal unsaturated polyethylene (E- 1) After charging 5.0 g and 500 ml of xylene, the temperature was raised to 95 ° C. to dissolve the macromonomers (P-2 and E-1). Thereto, ethylene 120 liter / hr and propylene 16.8 liter / hr were continuously fed to saturate the liquid phase and the gas phase. Subsequently, 6.0 mL (6.0 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al) in a state where ethylene and propylene were continuously supplied, and toluene of the compound (2) 10.0 mL (0.020 mmol) of the solution (0.0020 mol / L), and then a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) (4. 12.5 mL (0.050 mmol) was added, and polymerization was performed at 95 ° C. for 30 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol.

  The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 34.3 g of an olefin resin. Table 3 shows the analysis results of the olefin resin (β-8).

  The resin (β′-2) obtained by polymerizing in the same manner as in Example 8 except that the terminal unsaturated polypropylene (P-2) and the terminal unsaturated polyethylene (E-1) are not added is the method described above. Table 4 shows the results of analysis. This resin (β′-2) was assumed to be a copolymer constituting the main chain of the olefin resin (β-8).

[Example 9]
Step (C): Production of Olefin Resin (β-9) Into a 1 L glass reactor sufficiently purged with nitrogen, 5.0 g of terminal unsaturated polypropylene (P-2) and terminal unsaturated polyethylene (E- 1) After charging 5.0 g and 500 ml of xylene, the temperature was raised to 95 ° C. to dissolve the macromonomers (P-2 and E-1). Then, 120 liter / hr of ethylene was continuously supplied to saturate the liquid phase and the gas phase. Subsequently, in a state where ethylene was continuously supplied, 10.0 mL of 1-octene, 1.0 mL (1.0 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al), and the compound ( 2) toluene solution (0.0020 mol / L) in 5.0 mL (0.010 mmol), then triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) in toluene 0.63 mL (0.050 mmol) of the solution (4.0 mmol / L) was added, and polymerization was performed at 97 ° C. for 40 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol.

  The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 34.0 g of an olefin resin. Table 3 shows the analysis results of the olefin resin (β-9).

  The resin (β′-3) obtained by carrying out polymerization in the same manner as in Example 9 except that the terminal unsaturated polypropylene (P-2) and the terminal unsaturated polyethylene (E-1) are not added is the method described above. Table 4 shows the results of analysis. This resin (β′-3) was assumed to be a copolymer constituting the main chain of the olefin resin (β-9).

[Comparative Example 1]
Production of Olefin Resin (β′-1) Example 1 except that the step (C) was carried out by polymerization without adding terminal unsaturated polypropylene (P-1) and terminal unsaturated polyethylene (E-1). An olefin resin was produced in the same manner as described above. The obtained olefin resin (β′-1) was 24.2 g. Table 3 shows the analysis results of the obtained olefin resin (β′-1).

[Comparative Example 2]
Production of Olefin Resin (β′-4) Olefin as in Comparative Example 1 except that step (C) was carried out with the amount of 1-butene fed changed to 16 liters / hr and the polymerization temperature changed to 102 ° C. Based resin was produced. The obtained olefin resin (β′-4) was 21.4 g. The analysis results of the obtained olefin resin (β′-4) are shown in Tables 3 and 4.

[Comparative Example 3]
Production of Olefin Resin (β ″ -1) An olefin resin was produced in the same manner as in Example 2 except that the step (C) was carried out by polymerization without adding terminal unsaturated polyethylene (E-1). The obtained olefin resin (β ″ -1) was 32.9 g. Table 3 shows the analysis results of the resulting olefin resin (β ″ -1).

  According to the adhesive strength test, it can be seen that the olefin resin β obtained in Examples 1 to 9 can peel the two-layer sheet pressure-bonded under the above conditions with a weak force of 10 N / 80 mm or less, and is less sticky. On the other hand, the ethylene / α-olefin copolymer having no side chain obtained in Comparative Examples 1 and 2 could not be peeled off because the two-layer sheets were fused. Moreover, in the case of the resin containing the polymer having only the polypropylene side chain without including the polymer having both the polypropylene side chain and the polyethylene side chain obtained in Comparative Example 3, the adhesive force suppressing effect is sufficient. Instead, a peel strength of 12 N / 80 mm was required. From this, it can be seen that inclusion of a polymer having a side chain composed of an ethylene polymer is important in suppressing stickiness.

[Production Example 1]
Production of propylene-based homopolymer resin (α-h-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 at 130 ° C. for 2 hours. To obtain a homogeneous solution. 21.3 g of phthalic anhydride was added to the solution, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of the homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After completion of the dropwise addition, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Reacted.

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

Here, the free titanium compound was detected by the following method. 10 ml of the washing solution of the solid titanium catalyst component was collected with a syringe and placed in a 100 ml branch schlenk previously purged with nitrogen. Next, hexane was dried under 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 is passed through a filter paper and transferred to a 100 ml volumetric flask. Subsequently, 1 ml of concentrated H ₃ PO ₄ is added as a masking agent for iron (II) ions and 5 ml of 3% H ₂ O ₂ is added as a coloring agent for titanium, followed by ion exchange. The volume was made up to 100 ml with water. The volumetric flask was shaken and after 20 minutes, absorbance at 420 nm was observed using a UV measuring device. The free titanium was washed away until this absorption was not observed.

  The solid titanium catalyst component 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 was 2.3 mass% titanium, 61 mass% chlorine, 19 mass% magnesium, and 12.5 mass% DIBP.

(2) Production of prepolymerization catalyst 100 g of the solid titanium catalyst component, 39.3 mL of triethylaluminum, and 100 L of heptane were placed in an autoclave equipped with a stirrer having an internal volume of 200 L. While maintaining the internal temperature at 15 to 20 ° C., 600 g of propylene was added and reacted while stirring for 60 minutes to obtain a catalyst slurry containing a prepolymerized catalyst.

(3) Main polymerization In a jacketed circulation tubular polymerizer having an internal capacity of 58 L, propylene is 40 kg / hour, hydrogen is 223 NL / hour, and the catalyst slurry produced in (2) is 0.54 g / hour as a solid catalyst component. Triethylaluminum was continuously supplied at a rate of 2.4 ml / hour and dicyclopentyldimethoxysilane was continuously supplied at a rate of 0.84 ml / hour, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.57 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerization was performed. Propylene was supplied to the polymerization vessel at 16 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 6.3 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.30 MPa / G.

  The obtained propylene homopolymer resin (α-h-1) was vacuum-dried at 80 ° C. Regarding the physical properties of the propylene homopolymer resin (α-h-1), the melt flow rate (MFR) was 55 g / 10 min, and the isotactic pentad fraction (mmmm) was 97.8%.

[Production Example 2]
Production of propylene homopolymer resin (α-h-2) (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 at 130 ° C. for 2 hours. Then, 21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve the phthalic anhydride.

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

  After completion of the reaction for 2 hours, the 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 completion of the reaction, the solid part 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 solution of the above solid catalyst component was collected with a syringe and placed in a 100 ml 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 is passed through a filter paper and transferred to a 100 ml volumetric flask. Subsequently, 1 ml of concentrated H ₃ PO ₄ is added as a masking agent for iron (II) ions and 5 ml of 3% H ₂ O ₂ is added as a coloring agent for titanium, followed by ion exchange. The volume was made up to 100 ml with water. The volumetric flask was shaken and after 20 minutes, absorbance at 420 nm was observed using a UV measuring device. The free titanium was washed away until this absorption was not observed.

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

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

(3) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 43 kg / hour, hydrogen is 177 NL / hour, the catalyst slurry produced in (2) is 0.58 g / hour as a solid catalyst component, triethylaluminum Was continuously fed at a rate of 3.1 ml / hour and dicyclopentyldimethoxysilane at 3.3 ml / hour, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.53 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion 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-h-2) was vacuum dried at 80 ° C. As for the physical properties of the propylene homopolymer resin (α-h-2), the melt flow rate (MFR) was 30 g / 10 minutes, and the isotactic pentad fraction (mmmm) was 97.8%.

[Example 10]
23 parts by mass of the olefin resin (β-2) produced in Example 2, 57 parts by mass of the propylene homopolymer resin (α-h-1) produced in Production Example 1, talc (trade name: JM- 209, manufactured by Asada Flour Milling Co., Ltd.) 20 parts by mass, heat resistance stabilizer IRGANOX 1010 (trade name, manufactured by BASF Japan) 0.1 part by mass, heat resistance stabilizer IRGAFOS 168 (trade name, manufactured by BASF Japan) 0 After mixing 1 part by mass and 0.1 part by mass of calcium stearate with a tumbler, the mixture was melt-kneaded with a twin screw extruder under the following conditions to prepare a pellet-shaped propylene resin composition. Using the pellet-shaped propylene-based resin composition, an injection molding machine was used for injection molding under the following conditions to prepare a test piece. Table 5 shows the physical properties of the resulting propylene-based resin composition.

<Melting and kneading conditions>
Same-direction twin-screw kneader: KZW-15 (trade name, manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 40 rpm
<JIS small test piece / injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds.

[Example 11]
Example 10 is the same as Example 10 except that 23 parts by mass of the olefin resin (β-4) produced in Example 4 was used instead of 23 parts by mass of the olefin resin (β-2) produced in Example 2. Similarly, a propylene resin composition was prepared. Table 5 shows the physical properties of the resulting propylene-based resin composition.

[Example 12]
Example 10 is the same as Example 10 except that 23 parts by mass of the olefin resin (β-6) produced in Example 6 was used instead of 23 parts by mass of the olefin resin (β-2) produced in Example 2. Similarly, a propylene resin composition was prepared. Table 5 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 4]
20 parts by mass of the olefin resin (β′-4) produced in Comparative Example 2, 60 parts by mass of the propylene homopolymer resin (α-h-1) produced in Production Example 1, talc (trade name: JM -209, manufactured by Asada Flour Milling Co., Ltd.) 20 parts by mass, heat stabilizer IRGANOX 1010 (trade name, manufactured by BASF Japan) 0.1 part by mass, thermal stabilizer IRGAFOS168 (trade name, manufactured by BASF Japan) After mixing 0.1 part by mass and 0.1 part by mass of calcium stearate with a tumbler, the mixture was melt-kneaded with a twin screw extruder under the following conditions to prepare a pellet-shaped propylene resin composition. Using the pellet-shaped propylene-based resin composition, an injection molding machine was used for injection molding under the following conditions to prepare a test piece. Table 5 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 5]
23 parts by mass of 20 parts by mass of the olefin resin (β′-4) produced in Comparative Example 2 and 57 parts by mass of 60 parts by mass of the propylene homopolymer resin (α-h-1) produced in Production Example 1 A propylene resin composition was prepared in the same manner as in Comparative Example 4 except that the amount was changed to parts by mass. Table 5 shows the physical properties of the resulting propylene-based resin composition.

  The propylene resin composition containing the olefin resin (β) obtained in Examples 10 to 12 is a propylene resin containing the ethylene / α olefin copolymer resin having no side chain obtained in Comparative Examples 4 to 5. Compared with the composition, it is excellent in elongation physical properties, high hardness, and also excellent in the balance between rigidity and impact resistance. Since the olefin resin (β) has a side chain composed of a propylene polymer, it is presumed that the compatibility with the propylene polymer resin (α) is good and the balance of physical properties is improved. The

[Example 13]
5 parts by mass of olefin resin (β-6) produced in Example 6, 20 parts by mass of linear low density polyethylene resin (Evolue SP0510 (trade name, Prime Polymer Trademark)), produced in Production Example 2 75 parts by mass of the propylene-based homopolymer resin (α-h-2), heat resistance stabilizer IRGANOX1010 (trade name, manufactured by BASF Japan Ltd.), 0.1 part by mass, heat resistance stabilizer IRGAFOS168 (trade name, BASF Japan) (Made by Co., Ltd.) 0.1 parts by mass, calcium stearate 0.1 parts by mass, crystallization nucleating agent Millard NX8000 (trade name, Milliken Japan Co., Ltd.) 0.2 parts by mass was mixed with a tumbler and then biaxial. A pellet-shaped propylene resin composition was prepared by melt-kneading in an extruder under the following conditions. Using the pellet-shaped propylene-based resin composition, an injection molding machine was used for injection molding under the following conditions to prepare a test piece. Table 6 shows the physical properties of the resulting propylene-based resin composition.

<Melting and kneading conditions>
Same-direction twin-screw kneader: KZW-15 (trade name, manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 40 rpm
<JIS small test piece / injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

[Comparative Example 6]
Example 13 except that 5 parts by mass of the olefin resin (β′-4) produced in Comparative Example 2 was used instead of 5 parts by mass of the olefin resin (β-6) produced in Example 6. A propylene resin composition was prepared in the same manner as described above. Table 6 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 7]
25 parts by mass of a linear low density polyethylene resin (Evolue SP0510 (trade name, Prime Polymer Trademark)), 75 parts by mass of the propylene homopolymer resin (α-h-2) produced in Production Example 2, Thermal stabilizer IRGANOX 1010 (trade name, manufactured by BASF Japan) 0.1 mass part, thermal stabilizer IRGAFOS168 (trade name, manufactured by BASF Japan) 0.1 mass part, calcium stearate 0.1 mass part, After mixing 0.2 parts by mass of the crystallization nucleating agent Millard NX8000 (trade name, Milliken Japan Co., Ltd.) with a tumbler, the mixture is melt-kneaded with a twin screw extruder under the following conditions to form a pellet-shaped propylene resin composition. A product was prepared. Using the pellet-shaped propylene-based resin composition, an injection molding machine was used for injection molding under the following conditions to prepare a test piece. Table 6 shows the physical properties of the resulting propylene-based resin composition.

<Melting and kneading conditions>
Same-direction twin-screw kneader: KZW-15 (trade name, manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 40 rpm
<JIS small test piece / injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds

  The resin composition containing the olefin resin (β) obtained in Example 13 is superior in impact resistance as compared with the resin compositions obtained in Comparative Example 6 and Comparative Example 7. Since the olefin resin (β) includes a polymer having both a side chain composed of a propylene polymer and a side chain composed of an ethylene polymer, both the ethylene resin and the propylene polymer resin are included. It is inferred that the above-mentioned good physical properties were developed.

Claims (14)

Graft type heavy having a main chain (MC) composed of an ethylene / α-olefin copolymer, a side chain (SE) composed of an ethylene polymer, and a side chain (SP) composed of a propylene polymer An olefin resin (β) containing the coalescence [R1] and satisfying the following requirement (I).
(I) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5 dl / g. The olefin resin (β) according to claim 1, which satisfies the following requirement (II).
(II) In differential scanning calorimetry, a melting point (Tm) is observed in the range of 80 to 170 ° C. The olefin resin (β) according to claim 1 or 2, which satisfies the following requirement (III).
(III) The glass transition temperature (Tg) measured with a differential scanning calorimeter is in the range of −80 to −30 ° C. The olefin resin (β) according to any one of claims 1 to 3, which satisfies the following requirement (IV).
(IV) The proportion of repeating units derived from ethylene is in the range of 10 to 80 mol% with respect to all repeating units, and the proportion of repeating units derived from propylene is in the range of 2 to 80 mol% with respect to all repeating units. The olefin resin (β) according to any one of claims 1 to 4, wherein the graft polymer [R1] satisfies the following requirement (i).
(I) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain (SP) is 93% or more. The olefin resin (β) according to any one of claims 1 to 5, wherein the graft polymer [R1] satisfies at least one of the following requirements (ii) or (iii).
(Ii) The ethylene / α-olefin copolymer constituting the main chain (MC) has a repeating unit derived from ethylene and at least one α selected from α-olefins having 3 to 20 carbon atoms. -It has a repeating unit derived from an olefin in the range of 5 to 50 mol% in the main chain (MC).
(Iii) The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain (MC) is 10,000 to 500,000. The olefin resin (β) according to any one of claims 1 to 6, wherein the graft polymer [R1] satisfies the following requirements (iv) to (vii).
(Iv) The ethylene polymer constituting the side chain (SE) has a repeating unit derived from ethylene in the range of 95 to 100 mol% in the side chain (SE), and an α-olefin having 3 to 20 carbon atoms. In the side chain (SE) in the range of 0 to 5 mol%.
(V) The weight average molecular weight of the ethylene polymer constituting the side chain (SE) is in the range of 1,000 to 30,000.
(Vi) The propylene-based polymer constituting the side chain (SP) has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain (SP), and ethylene and α having 4 to 20 carbon atoms. -It has a repeating unit derived from at least one α-olefin selected from olefins in the range of 0 to 5 mol% in the side chain (SP).
(Vii) The propylene-based polymer constituting the side chain (SP) has a weight average molecular weight of 5,000 to 100,000.   2 or more types of transition metal compounds are used, The manufacturing method of the olefin resin ((beta)) as described in any one of Claims 1-7 characterized by the above-mentioned. The manufacturing method of the olefin resin ((beta)) of Claim 8 including the process of following (A), (B) and (C).
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process (B) The process of superposing | polymerizing ethylene in presence of the catalyst for olefin polymerization containing the transition metal compound [B] of the periodic table group 4 or 5 which has an organic ligand, and manufacturing terminal unsaturated polyethylene ( C) terminal unsaturated polypropylene produced in step (B) and terminal unsaturated polypropylene produced in step (B) in the presence of a catalyst for olefin polymerization containing a transition metal compound [C] belonging to Group 4 of the periodic table. A step of copolymerizing polyethylene, ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms.   2 to 98 parts by mass of propylene resin (α-1) and 2 to 98 parts by mass of olefin resin (β) according to any one of claims 1 to 7 (propylene resin (α-1) and olefin) A propylene-based resin composition, comprising: 100 parts by mass of the total of the resin (β).   50 to 98 parts by mass of the propylene resin (α-1) and 2 to 50 parts by mass of the olefin resin (β) (the total of the propylene resin (α-1) and the olefin resin (β) is 100 parts by mass. The propylene-based resin composition according to claim 10, comprising:   2 to 98 parts by mass of ethylene resin (α-2) and 2 to 98 parts by mass of olefin resin (β) according to any one of claims 1 to 7 (ethylene resin (α-2) and olefin) An ethylene-based resin composition comprising: 100 parts by mass of the total of the resin (β).   A resin composition comprising a propylene resin (α-1), an ethylene resin (α-2), and the olefin resin (β) according to any one of claims 1 to 7.   The molded object obtained from the resin composition as described in any one of Claims 10-13.