JP2019089921A - Propylene-based resin composition and method for producing the same, and molding using the propylene-based resin composition - Google Patents

Abstract

To provide a propylene-based resin composition excellent in balance among rigidity, impact resistance and hardness.SOLUTION: A propylene-based resin composition contains 70 pts.mass or more and less than 80 pts.mass of a propylene-based polymer (α) having a melt flow rate (MFR) at 230°C and a load of 2.16 kg, which is obtained in accordance with ASTM D1238E, of 0.1-500 g/10 min, and more than 20 pts.mass and 30 pts.mass or less of an olefin-based resin (β) satisfying specific requirements other than the propylene-based polymer (α), in which the total of the propylene-based polymer (α) and the olefin-based resin (β) is 100 pts.mass, where the resin composition contains 0-30 pts.mass of an inorganic filler to 100 pts.mass of the total of α and β, and flexural modulus measured in accordance with JIS K 7171 is within a range of 600-2,500 MPa.SELECTED DRAWING: None

Description

  The present invention relates to a propylene-based resin composition, a method for producing the same, and a molded article using the propylene-based resin composition.

  Polypropylene resin is used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electric parts, automobile parts, etc., and various modifiers according to the required performance. And propylene-based resin compositions containing additives. In addition, as efforts to 3R (Reduce, Reuse, Recycle) to form a recycling society, weight reduction by thin-walled molded articles has recently been attempted in each industrial field. Therefore, improvement of the propylene-based resin composition is advanced so that sufficient rigidity and impact resistance can be obtained even if the molded article is reduced in weight or thinned.

  Generally, a soft olefin resin composed of an ethylene / α-olefin copolymer is blended as a modifier of polypropylene resin. For further improvement of performance, it is applied as a modifier of olefin block polymer in which a crystalline polyethylene segment and an amorphous or low crystalline ethylene / α-olefin copolymer segment are chemically bonded to each other. There is hope.

  As a technology relating to such an olefin-based block polymer, a technology relating to a linear block polymer composed of a polyethylene segment obtained using the living polymerization catalyst disclosed in Patent Document 1 and an ethylene / α-olefin-based copolymer segment, There is a technology related to a polymer having a multiblock structure utilizing reversible chain transfer reaction between two catalysts disclosed in Patent Document 2.

  Apart from such linear block polymers, Patent Documents 3 to 8 have a graft type copolymer consisting of main chains and side chains, one of which is a soft segment and the other of which is a hard segment. A method has been proposed to obtain coalescence. In these disclosures, generally, a hard segment such as polyethylene having a vinyl group at the end is synthesized, and subsequent to the synthesis or simultaneously with the synthesis, the hard segment such as polyethylene is ethylene or an α- of 3 or more carbon atoms. Copolymerization with olefins is based on the technology of introducing into the soft segment which is the main chain.

  Patent Documents 3 and 4 disclose methods of copolymerizing terminal vinyl polyethylene produced using a specific metallocene catalyst with ethylene to obtain a grafted olefin polymer. According to the disclosed technology, although polyethylene having a vinyl group at the end is obtained, the terminal vinyl generation efficiency is low, and a large amount of polyethylene not taken in as a side chain remains. Therefore, when the graft type olefin polymer is blended in a polypropylene resin, unreacted polyethylene contained in a large amount deteriorates mechanical properties such as impact resistance. Thus, there is room for improvement in the performance of the graft type olefin polymer as a modifying resin, and even if the graft type olefin polymer is used, a polypropylene resin composition which expresses desired physical properties has not been obtained.

  On the other hand, Patent Documents 5 to 7 disclose a technique for synthesizing a terminal vinyl polyethylene for side chain at a high production rate by using a specific nonmetallocene complex as a catalyst. However, when the inventors conducted additional tests using the catalyst for forming a main chain disclosed in the examples of Patent Documents 5 and 7, a certain amount of terminal vinyl polyethylene is copolymerized in the main chain. However, it was confirmed that the uptake of terminal vinyl polyethylene was poor. Since the amount of side chain introduction is also limited in the block polymer obtained in this manner, its reforming performance is insufficient even if it is intended to utilize the block polymer as a polypropylene modifying resin. Although the method of introduce | transducing a side chain with high efficiency is disclosed by patent document 8 by using a co-supported catalyst, since a principal chain is limited to a crystalline polymer, the improvement of propylene-type resin is carried out. It has been difficult to produce polymers of amorphous or low crystalline regions suitable for quality applications.

JP 2007-84806 A JP, 2012-237013, A Japanese Patent Publication No. 1996-502303 Japanese Patent Publication No. 2001-527589 Japanese Patent Laid-Open No. 2002-105132 Unexamined-Japanese-Patent No. 2007-39540 JP, 2007-39541, A JP, 2009-144148, A

  Thus, even if a block polymer or a graft polymer chemically linked with different polymers disclosed in the prior art is applied as a modifier of polypropylene resin, high impact resistance and hardness are maintained while maintaining high rigidity. At present, it has not been possible to obtain a propylene-based resin composition excellent in the balance of the above.

  An object of the present invention is to provide a propylene-based resin composition excellent in balance of rigidity, impact resistance and hardness, and a molded article using the propylene-based resin composition.

That is, the present invention relates to the following [1] to [8].
[1] 70 parts by mass or more of a propylene-based polymer (α) having a melt flow rate (MFR) at a load of 2.16 kg at 230 ° C. and 0.1 to 500 g / 10 min obtained according to ASTM D1238E Olefin resin (β) exceeding 20 parts by mass and 30 parts by mass or less (wherein the propylene-based polymer has a content of less than 10 parts by mass and satisfies the following requirements (I), (IV) and (V) The total amount of the polymer (α) and the olefin resin (β) is 100 parts by mass), and the inorganic filler is 0 to 30 parts by mass with respect to a total of 100 parts by mass of α and β The propylene-based resin composition which contains and the bending elastic modulus measured according to JISK7171 exists in the range of 600-2500 MPa.
(I) The olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene / α-olefin copolymer and a side chain made of an ethylene polymer.
(IV) Glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C.
(V) The intrinsic viscosity [粘度] measured in decalin at 135 ° C. is in the range of 0.1 to 12 dl / g.

[2] The propylene resin composition according to [1], wherein the olefin resin (β) further satisfies the following requirements (II) and (III).
(II) A melting peak is shown in the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC), and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The proportion E of the ortho-dichlorobenzene soluble component at 20 ° C. or less measured by cross fractionation chromatography (CFC) is 60 mass% or less.

[3] The propylene-based resin composition according to [1] or [2], wherein the weight-average molecular weight of the ethylene polymer constituting the side chain of the graft type olefin polymer [R1] is in the range of 500 to 10,000. object.
[4] The side chain is present at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain of the graft type olefin polymer [R1] in any of [1] to [3] Propylene-based resin composition as described above.
[5] The propylene-based resin composition according to any one of [1] to [4], wherein the olefin-based resin (β) further satisfies the following requirement (VI).
(VI) MFR of olefin resin (β) at 190 ° C. and a load of 2.16 kg obtained according to ASTM D 1238 E is M (g / 10 min), and olefin system measured in decalin at 135 ° C. When the intrinsic viscosity [η] of the resin (β) is H (g / dl), the value A represented by the following formula (Eq-1) is in the range of 30 to 280.
A = M / exp (−3.3H) (Eq-1)

[6] The method for producing a propylene-based resin composition according to any one of [1] to [5], wherein the olefin-based resin (β) contains an ingredient of the following (A) to (C): It is characterized by being manufactured by a method comprising the step of copolymerizing ethylene and at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms in the presence of a polymerization catalyst Method of producing a propylene-based resin composition
(A) Bridged metallocene compound represented by the following formula (I) (B) Transition metal compound represented by the following formula [B] (C) (C-1) Organometallic compound, (C-2) organoaluminum oxy At least one compound selected from the group consisting of a compound, and (C-3) a compound which reacts with the bridged metallocene compound (A) or the transition metal compound (B) to form an ion pair

(In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group Two adjacent groups 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 the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-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 the group consisting of heteroatom-containing groups other than silicon-containing group and a silicon-containing group, an R ⁶ and R ⁷ are bonded to each other to form a ring R ¹⁰ and R ¹¹ may be combined with each other to form a ring, provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair And j each 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 as or different from each other. )

(In the formula [B],
M represents a transition metal atom of Group 4 or 5 of the periodic table.
m is an integer of 1 to 4;
R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms represented by the general formula C _{n ′} H _{2 n ′ + 1} (n ′ is an integer of 1 to 8).
R ^{2 to} R ⁵ each independently represent 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, a phosphorus containing group, a silicon containing A group, a germanium-containing group, or a tin-containing group is shown, and two or more of these may be bonded to each other to form a ring.
R ^{6 to} R ^{8 each} represent a hydrocarbon group, at least one of which is an aromatic hydrocarbon group, and when m is an integer of 2 or more, R may be R between structural units of the formula [B] ^Two groups among the groups represented by ^{2 to} R ⁸ may be linked.
n is a number satisfying the valence of M, 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, And X represents 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, plural Xs may be the same or different. In addition, a plurality of groups represented by X may be bonded to each other to form a ring. )

[7] The method for producing a propylene-based resin composition according to [6], wherein the step of copolymerization is a step of copolymerization by a solution polymerization method in a temperature range of 80 to 300 ° C.
[8] A molded article using the propylene resin composition according to any one of [1] to [5].

  According to the present invention, it is possible to provide a propylene-based resin composition excellent in the balance of rigidity, impact resistance and hardness, and a molded article using the propylene-based resin composition.

It is a photograph which shows the result of the damage resistance test of the propylene resin composition concerning Example 1 and Comparative Example 1. It is a photograph which shows the result of the damage resistance test of the propylene resin composition concerning Example 2 and Comparative Example 2.

  The propylene-based resin composition of the present invention is a propylene-based polymer having a melt flow rate (MFR) at a load of 2.16 kg at 230 ° C. of 0.1 to 500 g / 10 min obtained according to ASTM D1238E ( α) More than 20 parts by mass of an olefin resin (β) satisfying at least 70 parts by mass and less than 80 parts by mass, and the following requirements (I), (IV) and (V) other than the propylene polymer (α) 30 parts by mass The following is included (however, the total of 100 parts by mass of the propylene polymer (α) and the olefin resin (β) is 100 parts by mass), and the inorganic filler is added to 100 parts by mass of α and β in total: The material is characterized by containing 0 to 30 parts by mass, and the flexural modulus measured according to JIS K7171 is in the range of 600 to 2500 MPa. Hereinafter, the propylene-based polymer (α) and the olefin-based resin (β) contained in the propylene-based resin composition of the present invention will be described.

<Propylene-based polymer (α)>
The propylene-based polymer (α) is a homopolymer of propylene, a random copolymer of propylene and at least one selected from the group consisting of ethylene and α-olefins, or propylene with ethylene and α-olefins. It may be any block copolymer with at least one selected from the group consisting of Specific examples of the α-olefin 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, 1-decene, 1-o Decene, 1-dodecene, and the like can be given. Among these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  The melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg obtained according to ASTM D1238 E of a propylene-based polymer (α) is 0.1 to 500 g / 10 min, preferably 0.2 It is -400 g / 10 minutes, more preferably 0.3-300 g / 10 minutes. When the MFR of the propylene-based polymer (α) is lower than 0.1 g / 10 min, the dispersibility of the propylene-based polymer (α) and the olefin-based resin (β) in the propylene-based resin composition is deteriorated, Mechanical strength may decrease. In addition, when the MFR of the propylene-based polymer (α) is higher than 500 g / 10 min, the strength of the propylene-based polymer (α) itself decreases and the mechanical strength of the obtained propylene-based resin composition decreases. There is a case.

  The pentad fraction (mm mm (%)) of the propylene-based polymer (α) is preferably 90% or more, more preferably 95% or more. When the pentad fraction is in the above range, the rigidity of the propylene-based resin composition is excellent.

<Olefin resin (β)>
The olefin resin (β) is an olefin resin other than the propylene polymer (α), and satisfies all of the following requirements (I), (IV) and (V). Moreover, it is preferable that olefin resin ((beta)) satisfy | fills all the following requirements (I)-(V). In addition, an olefin resin ((beta)) may be comprised from 1 type of olefin resin, and may be comprised from 2 or more types of olefin resins.
(I) The olefin-based resin (β) includes a graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer.
(II) A melting peak is shown in the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC), and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The proportion E of the ortho-dichlorobenzene soluble component at 20 ° C. or less measured by cross fractionation chromatography (CFC) is 60 mass% or less.
(IV) Glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C.
(V) The intrinsic viscosity [粘度] measured in decalin at 135 ° C. is in the range of 0.1 to 12 dl / g.
Hereinafter, these requirements (I) to (V) will be specifically described.

[Requirement (I)]
The olefin-based resin (β) has a graft type olefin-based polymer [R1] (hereinafter referred to as “olefin-based polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer ] Is included. The olefin-based resin (β) contains the olefin-based polymer [R1] as an essential component by being produced using, for example, a polymerization method described later. The olefin polymer [R1] is a graft copolymer having a main chain and a side chain. In the present invention, the term "graft copolymer" means a T-type polymer or a comb polymer in which one or more side chains are bonded to the main chain. However, in the side chain, monomer units other than ethylene can be contained in the range which does not deviate from the meaning of the present invention.

  As described above, the olefin polymer [R1] has a crystalline side chain structure despite the fact that the main chain structure is an amorphous or low crystalline ethylene copolymer. The olefin-based resin (β) according to the invention is less sticky than general ethylene-based elastomers, such as ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc., and product pellets The handling property of is good.

It is preferable that the main chain and the side chain of the olefin polymer [R1] satisfy at least one of the requirements selected from the group consisting of the following requirements (i) to (v).
(I) Ethylene / α-olefin copolymer of a main chain with a unit derived from ethylene and a unit derived from at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms And contains 60 to 97 mol% of units derived from ethylene and 3 to 40 mol% of units derived from α-olefin.
(Ii) The weight-average molecular weight of the ethylene / α-olefin copolymer constituting the main chain is in the range of 20,000 to 400,000.
(Iii) The side chain consists essentially of units derived from ethylene.
(Iv) The weight average molecular weight of the ethylene polymer constituting the side chain is in the range of 500 to 10,000.
(V) Side chains are present at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain.
Hereinafter, these requirements (i) to (v) will be specifically described.

(Requirement (i))
The main chain of the olefin polymer [R1] is an ethylene / α-olefin copolymer, and is a site responsible for characteristics such as flexibility and low temperature characteristics as a modifier. Therefore, the main chain of the olefin polymer [R1] comprises a unit derived from ethylene and a unit derived from at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms. It is preferable that it is an ethylene-alpha-olefin copolymer.

  Here, specific examples of the α-olefin having 3 to 20 carbon atoms which is copolymerized with ethylene include propylene, 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-pethene Ten, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, it can be mentioned 1-dodecene and the like.

  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, 4-methyl-1-pentene, 3-methyl-1-pentene, Branched olefins such as 3-methyl-1-butene are preferred, and propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are more preferred.

  The molar ratio of units derived from ethylene in the main chain of the olefin polymer [R1] to units derived from all monomers is preferably 60 to 97 mol%, more preferably 60 to 95 mol%, still more preferably 65 to 90 mol%, Particularly preferably, it is 65 to 85 mol%. The molar ratio (α-olefin composition) of the unit derived from α-olefin in the main chain to the unit derived from all monomers is preferably 3 to 40 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 35 mol. %, Particularly preferably 15 to 35 mol%.

  When the molar ratio of units derived from ethylene and α-olefin in the main chain is in the above range, the olefin resin (β) is rich in flexibility and has excellent low-temperature properties. Therefore, the propylene-based resin composition of the present invention containing the olefin-based resin (β) is excellent in low-temperature impact resistance. On the other hand, when the unit derived from α-olefin is less than 3 mol%, the obtained olefin resin becomes a resin inferior in flexibility and low temperature characteristics, so a propylene resin composition containing the resin tends to be inferior in low temperature impact resistance There is. In addition, when the molar ratio of units derived from α-olefin exceeds 40 mol%, it works disadvantageously in copolymerizing the macromonomer forming the side chain described later, so the effect by the graft polymer described later is not exhibited, It tends to be a propylene-based resin composition which is inferior in balance of physical properties of impact resistance and rigidity.

The molar ratio of units derived from ethylene and α-olefin in the main chain is adjusted by controlling the ratio of the concentration of ethylene to the concentration of α-olefin present in the polymerization reaction system in the step of producing the main chain. it can. The molar ratio (mol%) of units derived from α-olefin contained in the main chain, that is, the α-olefin composition in the main chain can be calculated or defined by the following method (1) or (2).
(1) The alpha-olefin composition of the component which consists only of ethylene-alpha-olefin copolymer byproduced in the manufacturing process of an olefin resin ((beta)) is defined as a unit derived from the alpha-olefin of a principal chain. Since the by-produced ethylene / α-olefin copolymer corresponds to a soluble component at a temperature of 20 ° C. or less when the olefin resin (β) is charged in ortho-dichlorobenzene, the soluble component The alpha-olefin composition in can be calculated | required by calculating by the well-known method using carbon nuclear magnetic resonance analysis (< ¹³ > C-NMR).
(2) A polymer having only a main chain site is separately synthesized under rational conditions in light of the production conditions of the olefin resin (β), and the α-olefin composition of the obtained ethylene / α-olefin copolymer is By analysis, it is indirectly defined as the α-olefin composition of the main chain of the olefin polymer [R1]. With rational conditions, a polymer equivalent to the main chain site of olefin polymer [R1] is generated in principle, such as the concentration of ethylene and α-olefin in the polymerization system, the molecular abundance ratio of ethylene and hydrogen, etc. It is a condition. In particular, as a method of producing an olefin resin (β), a method of producing an ethylene polymer site (macromonomer) corresponding to a side chain in advance and copolymerizing the macromonomer with ethylene and an α-olefin In the case where is adopted, the polymerization is separately conducted under the same conditions except that the macromonomer is not added, and indirectly by analyzing the α-olefin composition of the obtained ethylene / α-olefin copolymer. It defines as the alpha-olefin composition of the principal chain of olefin system polymer [R1].

(Requirement (ii))
The weight-average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the olefin polymer [R1] is preferably in the range of 20000 to 400000, more preferably 30000 to 300000, still more preferably 50000 It is in the range of ̃200,000.

  When the weight average molecular weight of the main chain is in the above range, the propylene-based resin composition of the present invention containing the olefin-based resin (β) exhibits a better balance of impact resistance, rigidity and hardness. On the other hand, when the weight average molecular weight of the main chain is less than 20000, impact resistance and toughness may be reduced. In addition, when the weight average molecular weight of the main chain exceeds 400000, poor dispersion in a propylene-based resin tends to occur, making it difficult to obtain a desired balance of physical properties.

  The weight average molecular weight of the main chain can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described later. As a control method of ethylene concentration, adjustment of ethylene partial pressure adjustment and adjustment of polymerization temperature are mentioned. The weight average molecular weight of the main chain can also be adjusted by supplying hydrogen into the polymerization system.

  In addition, the weight average molecular weight of the main chain is obtained by obtaining an ethylene / α-olefin copolymer according to the method of calculating or defining the molar ratio (mol%) of units derived from α-olefin in the above-mentioned “Requirement (i)” It can obtain | require by measuring the weight average molecular weight of the said copolymer by a conventional method. For example, the weight average molecular weight of the main chain can be determined from the weight average molecular weight in terms of polyethylene, which is determined by gel permeation chromatography (GPC).

(Requirement (iii))
The side chain of the olefin polymer [R1] is an ethylene polymer consisting essentially of units derived from ethylene, and consists of a crystalline ethylene polymer chain.

  The ethylene polymer consisting essentially of units derived from ethylene preferably has a molar ratio of units derived from ethylene of 95.0 to 100 mol%, based on the units derived from all the monomers contained in the ethylene polymer. The polymer is preferably 98.0 to 100 mol%, more preferably 99.5 to 100 mol%. That is, you may contain alpha-olefins other than ethylene in the range which does not impair the role and the characteristic.

  The side chain of the olefin-based polymer [R1] acts as a physical crosslinking point in the olefin-based resin (β), and plays a role in surface hardness improvement and rigidity enhancement in the propylene-based resin composition. That the side chain is a crystalline ethylene polymer chain means that a melting peak is observed in the range of 60 to 130 ° C. in differential scanning calorimetry (DSC) of the olefin resin (β) according to the present invention, That is, it can confirm by having melting temperature (Tm) in the range of 60-130 degreeC.

(Requirement (iv))
The weight-average molecular weight of the ethylene polymer constituting the side chain of the olefin polymer [R1] is preferably in the range of 500 to 10,000, more preferably 500 to 5,000, and still more preferably 500 to 3,000. It is.

  When the weight average molecular weight of the side chain is within the above range, the propylene resin composition containing the olefin resin (β) can exhibit high impact resistance while having high rigidity and high surface hardness. it can. When the weight average molecular weight of the side chain is less than 500, the role of the side chain component as a physical crosslinking point decreases, and the propylene resin composition containing an olefin resin (β) tends to have a reduced surface hardness and rigidity. There is. On the other hand, when the weight average molecular weight of the side chain exceeds 10000, the mechanical properties such as rigidity, surface hardness, and toughness of the propylene-based resin composition decrease due to a decrease in the number of side chains relative to the main chain, or ethylene · α− As the relative amount of olefin copolymer sites is reduced, the impact resistance may be reduced.

  The olefin polymer [R1] can be obtained by copolymerizing ethylene and an α-olefin with a macromonomer which is an ethylene polymer chain. That is, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the side chain of the olefin polymer [R1]. Therefore, the weight average molecular weight of the side chain is determined by analyzing the molecular weight of the ethylene-based polymer portion (macromonomer) separated as a soluble component on the low molecular weight side by GPC measurement of the olefin resin (β) It can be calculated by performing GPC measurement of the ethylene polymer site (macromonomer). Examples of the method of adjusting the weight average molecular weight of the side chain include a method of changing the type of transition metal compound used as a catalyst for forming a vinyl-terminated macromonomer described later, and a method of adjusting polymerization conditions.

(Requirement (v))
The side chain of the olefin polymer [R1] is preferably present at an average frequency (number of grafts) of 0.1 to 20 per 1000 carbon atoms (in the main chain polymer molecular chain) contained in the main chain. More preferably, it is present at an average frequency of 0.1 to 10, and more preferably at an average frequency of 0.2 to 5.

  The propylene-based resin composition containing the olefin-based resin (β) has high surface hardness and high rigidity while maintaining rigidity by the side chains being introduced into the main chain at an average frequency within the above range. Sex can be expressed. On the other hand, when the side chains are introduced into the main chain at an average frequency of less than 0.1, the effect of the physical crosslinking point due to the side chains is reduced, so the propylene resin composition containing the resin has rigidity It may decrease. In addition, when the side chain is introduced into the main chain at an average frequency of more than 20, the relative amount of the crystal component consisting of ethylene polymer sites becomes large, and therefore, the propylene-based resin composition containing the resin has an impact resistance. Gender may decrease.

The average frequency of the side chain can be calculated, for example, using [a] a method using an isotope carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) described later, or a method using [b] GPC. Hereinafter, methods [a] and [b] will be described.

[A] The olefin polymer [R1] is composed of a unit derived from at least one α-olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, and the main chain is an isotope carbon In the measurement by nuclear magnetic resonance spectrum ( ¹³ C-NMR), in the range of 37.8 to 38.1 ppm, the methine carbon at the junction of the side chain and the main chain separately from the methine carbon derived from the α-olefin Preferably, a signal attributable to

When the signal is observed, the side chain average frequency can be determined by the following equation.
[Side chain average frequency] = 1000 × [I _{PE -methine} ] / {[I _all-C ] × [(100- [R2 ′]-[M]) / 100}
[I _PE-methine ]: integral value of methine carbon at junction of side chain and main chain [I _all-C ]: total carbon integral value,
[R2 ′]: mass ratio (% by mass) in the olefin resin (β) of the polymer [R2] other than [R1] produced in the production of [R1]
[M]: [R1] mass ratio (% by mass) of the macromonomer added to or produced in the production of the olefin resin (β)

[B] As described above, the low molecular weight side peak obtained when analyzing the olefin resin (β) by GPC is the ethylene polymer site (macromonomer) remaining without copolymerization during the copolymerization reaction. It originates. Therefore, the mass ratio of the remaining macromonomer contained in the olefin resin (β) can be determined from the area ratio. When the mass composition of the macromonomer to be added or produced in the production of the olefin polymer [R1] is clear, the side chain average frequency can be determined from the difference between the mass composition and the mass ratio of the remaining macromonomer. Specifically, it can be determined by the following equation.
[Side chain average frequency] = ([M]-[M ']) / (100- [M']) × (1 / [Mn- _M ]) × 14 / {1-([M]-[M '] ] / (100- [M '])} × (1/1000)
[M]: mass ratio (% by mass) of the macromonomer added or produced in the production of [R1] to the total amount of resin [R '] obtained in the production of [R1] (% by mass)
[M ']: mass ratio (mass%) of the remaining macromonomer determined by GPC based on the total amount of resin [R'] obtained at the time of [R1] production (mass%)
[Mn- _M ]: Number average molecular weight of macromonomer

  In addition, the average frequency calculated | required by the said method [a] and [b] is a value when counting the said polymer as 0 side chain number, when the ethylene / alpha-olefin copolymer to byproduce exists. is there.

  The number of side chains can be adjusted by controlling the molar concentration of the macromonomer in the polymerization system. For example, when the side chain molecular weight is constant under a certain polymerization condition, the molar concentration of the macromonomer increases and the number of side chains of the graft polymer formed increases when the preparation mass or formation mass of the macromonomer is increased. . In addition, when the preparation mass or formation mass of the macromonomer is constant, the molar concentration of the macromonomer can be increased by decreasing the side chain molecular weight, and the number of side chains of the graft polymer to be formed can be increased. The number of side chains can also be adjusted by selecting the type of the bridged metallocene compound (A) described later, for example, a transition metal which exhibits high copolymerizability at high temperature and produces a polymer of high molecular weight. By selecting an olefin polymerization catalyst containing a compound, the number of side chains can be increased.

  The olefin-based polymer [R1] contained in the olefin-based resin (β) contains the olefin-based resin (β) by satisfying at least one of the requirements selected from the group consisting of (i) to (v). The characteristic that the propylene-based resin composition meets all the requirements for rigidity, hardness and impact resistance at a high level can be more significantly manifested. It is more preferable that the olefin polymer [R1] further satisfy the following requirement (vi).

(Requirement (vi))
The methyl branch number of the side chain of the olefin polymer [R1] is less than 0.1 per 1000 carbons contained in the side chain.

When the number of methyl branches in the side chain is in the above range, the crystallinity of the ethylene polymer portion in the side chain is further enhanced, and the propylene resin composition containing the olefin resin (β) has surface hardness and rigidity. Get higher. In addition, the number of methyl branches is an ethylene-based polymer portion (macromonomer) corresponding to a side chain separated as a soluble component on the low molecular weight side in GPC by the method described in “Requirement (iii)”, or previously synthesized A known method using isotope carbon nuclear magnetic resonance analysis ( ¹³ C-NMR), for example, described in JP-A-2006-233207, for the ethylene polymer moiety (macromonomer) corresponding to the side chain It can be measured by the following method. The side-chain ethylene polymer site satisfying the above requirements can be obtained by using a specific type of transition metal compound as a catalyst for producing a vinyl-terminated macromonomer described later.

[Requirement (II)]
The olefin resin (β) preferably exhibits an endothermic peak, ie, a melting peak (Tm) in the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC), and the heat of fusion calculated from the melting peak area It is preferable that (DELTA) H exists in the range of 3-100 J / g. The melting peak (Tm) is more preferably in the range of 80 to 125 ° C, still more preferably 90 to 120 ° C. The heat of fusion ΔH is more preferably in the range of 4 to 80 J / g, still more preferably 5 to 70 J / g, and particularly preferably 8 to 60 J / g.

  Tm and ΔH are crystallized by DSC after cooling up to 30 ° C. after melting the sample through DSC once, and endothermic peak appears in the second heating (10 ° C./min) It is an analysis.

  The melting temperature (Tm) and the heat of fusion ΔH observed in the above range are mainly derived from the side chain ethylene polymer of the olefin polymer [R1] constituting the olefin resin (β), and the melting temperature When the (Tm) and the heat of fusion ΔH are in the above ranges, the balance between the rigidity, the heat resistance and the toughness of the propylene resin composition of the present invention becomes good. On the other hand, when the melting temperature (Tm) or the heat of fusion ΔH is below the above range, the rigidity, heat resistance and toughness of the propylene resin composition are lowered. Moreover, when the heat of fusion ΔH exceeds the above range, the impact resistance of the propylene-based resin composition is lowered, which is not preferable.

  As a method of adjusting melting temperature (Tm) in the said range, the method of selecting suitably the kind of transition metal compound used for the catalyst for vinyl terminal macromonomer production mentioned later is mentioned. Further, as a method of adjusting the heat of fusion ΔH within the above range, a method of controlling the abundance ratio of the vinyl-terminated macromonomer in the production process described later can be mentioned. Specifically, it is a method of controlling the feed amount of the vinyl-terminated macromonomer or controlling the feed ratio of the bridged metallocene compound (A) and the transition metal compound (B) described later.

[Requirement (III)]
In the olefin resin (β), the proportion E (E value) of ortho-dichlorobenzene soluble components at 20 ° C. or less measured by cross fractionation chromatography (CFC) is preferably 60 mass% or less, more preferably It is 50% by mass or less, more preferably 45% by mass or less.

  Usually, commercially available ethylene / α-olefin copolymers, for example, ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / octene copolymers, etc., are α-olefins such as propylene, 1-butene or 1-octene. It is a polymer adjusted to have an olefin composition of about 10 to 50 mol%, exhibits non-crystallinity or low crystallinity, and dissolves well in a specific organic solvent even at temperatures below room temperature. For example, Toughmer (registered trademark) A-5055S (trade name), which is a commercially available ethylene / butene copolymer resin, is mostly soluble in orthodichlorobenzene at 20 ° C. or less, and has an E value of usually 93 mass. % Or more.

  On the other hand, the olefin polymer [R1] constituting the olefin resin (β) according to the present invention has a main chain of ethylene / α-olefin copolymer as described above and a side chain of crystalline ethylene Because it is united, it becomes poorly soluble in ortho-dichlorobenzene below room temperature. Therefore, the olefin resin (β) according to the present invention is characterized in that the E value is small. The fact that the olefin resin (β) has a small E value is an indirect evidence that the main chain structure and the side chain structure of the olefin polymer [R1] are chemically bonded, and further, It shows that the olefin polymer [R1] is contained in a considerable amount in the olefin resin (β).

  In the propylene-based resin composition of the present invention, the olefin-based resin (β) is dispersed in a polypropylene resin in the same manner as a commercially available ethylene / α-olefin copolymer resin generally used as a modifier, It plays the role of giving impact. Here, when a commercially available ethylene / α-olefin copolymer resin is used, while the impact resistance is improved according to the addition amount, the inherent rigidity and mechanical strength of polypropylene are reduced. On the other hand, when the olefin resin (β) according to the present invention is used, the polyethylene portion which is the side chain of the olefin polymer [R1] in the domain formed by the ethylene / α-olefin copolymer is physically crosslinked. The points are formed, and the domain itself is given high rigidity, hardness and mechanical strength. As a result, it is presumed that the propylene-based resin composition of the present invention is excellent in surface hardness, and the balance between rigidity and impact resistance is remarkably improved. Therefore, the fact that the olefin-based resin (β) contains a considerable amount of the olefin-based polymer [R1] is an important factor in expressing the good physical property balance of the polypropylene-based resin composition of the present invention.

  As already explained, the olefin resin (β) contains a considerable amount of a component in which a crystalline ethylene polymer moiety is chemically bonded to an ethylene / α-olefin copolymer, and therefore the above-mentioned requirements (II) and requirement (III) can be satisfied simultaneously. In order to obtain such an olefin resin (β), the selection of a catalyst used in the step of copolymerizing ethylene with an α-olefin and a terminal vinyl ethylene polymer is important. For example, a crosslinked metallocene compound (A) described later This can be achieved by using

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

  The glass transition temperature (Tg) is derived from the ethylene / α-olefin copolymer of the main chain of the olefin polymer [R1]. When the glass transition temperature (Tg) is in the range of −80 to −30 ° C., the propylene-based resin composition containing the olefin-based resin (β) exhibits a good impact resistance. The glass transition temperature (Tg) in the said range can be obtained by controlling the kind and composition of (alpha) -olefin which is a comonomer.

  The olefin copolymer [R1] contained in the olefin resin (β) has a main chain having a low glass transition temperature (Tg) and a side chain containing crystalline polyethylene. Therefore, when the olefin resin (β) is added to the propylene polymer (α), the low temperature impact property is exhibited by the main chain having a low Tg, and the rigidity by the side chain polyethylene component acting as a physical crosslinking point And hardness is well expressed. As a result, it is surmised that in the propylene-based resin composition, the balance between the low temperature impact property and the low linear expansion coefficient is remarkably improved while maintaining the rigidity.

[Requirement (V)]
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 12 dl / g, preferably 0.2 to 10 dl / g, more preferably 0 0.5-5 dl / g. When the intrinsic viscosity is in the above range, the propylene-based resin composition containing the olefin-based resin (β) exhibits good rigidity and mechanical strength in addition to impact resistance, and further achieves good moldability and processability. Do.

In addition to the requirements (I) to (V), the olefin resin (β) preferably further satisfies the following requirement (VI).
[Requirement (VI)]
Melt flow rate (MFR) at 190 ° C. and 2.16 kg load obtained according to ASTM D1238 E is M (g / 10 min), and the intrinsic viscosity [[] measured in decalin at 135 ° C. is H When (g / dl), the value A represented by the following formula (Eq-1) is preferably in the range of 30 to 280, more preferably in the range of 60 to 250, and still more preferably 70 to 200. Within the scope of
A = M / exp (−3.3H) (Eq-1)

  The fact that the olefin resin (β) has an A value within the above range indicates that the macromonomer introduction rate is high, and the olefin resin (β) satisfying the requirement (VI) is a modification of the propylene resin Even when applied to quality, it is preferable because it does not cause deterioration of physical properties such as rigidity caused by the remaining macromonomer and non-graft type polymer.

[Other physical properties of olefin resin (β)]
(Elastic modulus)
The modulus of elasticity of the olefin resin (β) is preferably in the range of 2 to 120 MPa, more preferably 3 to 100 MPa, and still more preferably 5 to 90 MPa. When the elastic modulus is in the above range, the propylene-based resin composition containing the olefin-based resin (β) is more excellent in the balance between the rigidity and the impact resistance. The olefin resin (β) is flexible because the main chain structure of the olefin polymer [R1] is composed of an ethylene / α-olefin copolymer. That is, the propylene-based resin composition containing the olefin-based resin (β) exhibits a good impact resistance. The elastic modulus is preferably a tensile elastic modulus in accordance with ASTM D638.

(Phase separation structure)
It is preferable that the phase which shows the crystalline component observed with a transmission electron microscope is a non-continuous phase of micrometer order of olefin resin ((beta)). In addition, observation of whether it has such a phase structure is implemented as follows, for example.

First, the propylene-based resin composition is preheated for 5 minutes using a hydraulic heat press molding machine set at 170 ° C., molded for 1 minute under 10 MPa pressure, and then 3 minutes under pressure of 10 MPa at 20 ° C. The specimen is obtained by cooling and producing a sheet of a predetermined thickness. The test sheet which is the above-mentioned press sheet is made into a piece of 0.5 mm square, and it is dyed with ruthenium acid (RuO ₄ ). Furthermore, with an ultramicrotome equipped with a diamond knife, the obtained pieces are made into ultrathin sections with a film thickness of about 100 nm. Carbon is deposited on this ultrathin section and observed with a transmission electron microscope (accelerating voltage 100 kV).

  According to this observation method, the side-chain ethylene polymer component of the olefin polymer [R1] has higher contrast because the intercrystalline non-crystalline site of the lamellar structure formed by the component is selectively stained with ruthenium acid. As observed. It is preferable that the phase which shows the crystalline component which consists of a side chain ethylene polymer of the olefin polymer [R1] which is observed in this way is a discontinuous phase of micrometer order as for an olefin resin ((beta)). As described above, since the olefin resin (β) is mainly composed of the olefin polymer [R1] in which the crystalline or low crystalline main chain and the crystalline side chain are linked by a covalent bond, the non-crystalline component is It is considered that the effect of the compatibilization between the crystalline component and the crystalline component is large, so that the microphase separation structure as described above is formed.

  The discontinuous phase observed in the olefin resin (β) is a physical crosslinking point consisting of a side chain ethylene polymer, and is formed in the propylene resin composition of the present invention using the olefin resin (β) It is considered that the physical crosslinking point is formed also in the ethylene / α-olefin copolymer domain. Therefore, as described above, the propylene-based resin composition of the present invention is considered to be excellent in the balance between the rigidity and the impact resistance.

  On the other hand, when a polymer blend of ethylene / α-olefin copolymer and ethylene polymer is used, the micro phase separation structure is not formed, and a coarse crystal phase is observed. Therefore, in a propylene-based resin composition using the polymer blend, no physical crosslinking point is formed in the olefin copolymer domain, and a propylene-based resin composition exhibiting a good balance of physical properties can not be obtained.

  As described above, the low molecular weight side peak obtained when analyzing the olefin resin (β) by GPC is derived from the ethylene polymer site (macromonomer) remaining without copolymerization during the copolymerization reaction, The composition ratio (mass ratio) of the remaining macromonomer contained in the olefin resin (β) can be determined from the area ratio of the low molecular weight side peak to the total peak area. The mass ratio of the remaining macromonomer is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, still more preferably 0 to 20% by mass, and particularly preferably 2 to 20% by mass. If the mass ratio of the remaining macromonomer is within the above range, it means that the component of the ethylene polymer alone not incorporated into the main chain is sufficiently small, whereby the olefin resin (β) is effective Can express the modification performance. On the other hand, when the mass ratio of the remaining macromonomer exceeds 30% by mass, not only the modification effect on impact resistance is inferior, but also the rigidity may be significantly reduced.

[Method of producing olefin resin (β)]
The production of the olefin resin (β) includes the steps of polymerizing ethylene to produce the macromonomer and the step of copolymerizing ethylene, an α-olefin and the macromonomer, which may be carried out sequentially , You may go at the same time. As a method for producing the olefin resin (β) of the present invention, for example, a method of polymerizing a specific olefin in the presence of an olefin polymerization catalyst used by combining the following components (A) to (C) may be mentioned: Can. Hereinafter, after demonstrating each component of (A)-(C), a specific manufacturing method, manufacturing conditions, etc. are demonstrated.

(Bridged Metallocene Compound (A))
The bridged metallocene compound (A) used in the present invention is represented by the following formula (I) and functions as a catalyst for olefin polymerization in the presence of a compound (C) described later.

(In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group Two adjacent groups 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 the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-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 the group consisting of heteroatom-containing groups other than silicon-containing group and a silicon-containing group, an R ⁶ and R ⁷ are bonded to each other to form a ring R ¹⁰ and R ¹¹ may be combined with each other to form a ring, provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair And j each 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 as or different from each other. )

  The olefin polymerization catalyst containing the bridged metallocene compound (A) comprises ethylene and at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms, and a transition metal compound described later It plays a role of copolymerizing a vinyl-terminated macromonomer synthesized by an olefin polymerization catalyst consisting of (B) and a compound (C) to form a main chain of the olefin polymer [R1].

  That is, an olefin polymerization catalyst comprising a bridged metallocene compound (A) can copolymerize ethylene, an α-olefin and a vinyl-terminated macromonomer, and in particular, a high co-polymer relative to the α-olefin and the vinyl-terminated macromonomer. It has the characteristic of showing the polymerizability. Furthermore, the catalyst for olefin polymerization containing a bridged metallocene compound (A) exhibits sufficiently high olefin polymerization activity even under relatively high temperature conditions where macromonomers of ethylene polymer chains dissolve, and is sufficiently high for practical use. It has the feature of producing a polymer of molecular weight.

  Since the olefin polymerization catalyst containing the crosslinked metallocene compound (A) has the above features, the olefin resin (β) contains a large amount of the olefin polymer [R1], and the above-mentioned requirement (I) , (IV) and (V), preferably (I) to (V) can be satisfied. As a result, the propylene-based resin composition of the present invention has a high surface hardness and an excellent balance of physical properties between impact resistance and rigidity. Hereinafter, features of the chemical structure of the bridged metallocene compound (A) used in the present invention will be described.

The bridged metallocene compound (A) has the following features [m1] to [m3] in terms of structure.
[M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other one is a fluorenyl group having a substituent (hereinafter referred to as “substituted fluorenyl group” It is also called).
[M2] The two ligands are linked by an aryl group-containing covalent bond bridge (hereinafter also referred to as "bridge") consisting of a carbon atom having an aryl (aryl) group or a silicon atom.
[M3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom or a hafnium atom.

  Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the crosslinked part, and other features which the bridged metallocene compound (A) has will be described in order.

(Cyclopentadienyl group which may have a substituent)
In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, Hydrogen and silicon containing groups are preferred. Two adjacent groups of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring.

For example, all of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, or any one or more of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group (hereinafter referred to as “carbonized” It may be referred to as hydrogen group (f1) or silicon-containing group (hereinafter referred to as "silicon-containing group (f2)"). As hetero atom containing groups other than the said silicon containing group, a halogenated hydrocarbon group, an oxygen containing group, a nitrogen containing group etc. can be mentioned.

  The hydrocarbon group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include a linear or branched hydrocarbon group such as an alkyl group, an alkenyl group and an alkynyl group; a cycloalkyl group and the like Examples thereof include cyclic saturated hydrocarbon groups; and cyclic unsaturated hydrocarbon groups such as aryl groups. The hydrocarbon group (f1) also includes a group in which any two hydrogen atoms bonded to carbon atoms adjacent to each other among the groups exemplified above are simultaneously substituted to form an alicyclic or aromatic ring.

  As the hydrocarbon group (f1), specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Linear hydrocarbon groups such as n-nonyl group, n-decanyl group, allyl (allyl) group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl , 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantine Cyclic saturated hydrocarbon groups such as aryl groups; aryl groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group, and cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, indenyl group, fluorenyl group and the like Nuclear alkyl substitution products; groups in which at least one hydrogen atom possessed by a saturated hydrocarbon group, such as benzyl group and cumyl group, is substituted with an aryl group can be mentioned.

  The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms, and examples thereof include a group in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group. Specific examples thereof include an alkylsilyl group such as a trimethylsilyl group, and an arylsilyl group such as a triphenylsilyl group.

  Specific examples of the hetero atom-containing group other than the silicon-containing group (f2) include methoxy group, ethoxy group, phenoxy group, N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, A pentafluorophenyl group is mentioned.

When two or more of R ¹ , R ² , R ³ and R ⁴ are substituents other than a hydrogen atom, the substituents may be the same or different. Further, two adjacent groups of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form an alicyclic or aromatic ring.

(Substituted fluorenyl group)
In formula (I), R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and a hydrogen atom or carbonization Hydrogen and silicon containing groups are preferred. R ⁶ and R ^{11 each} represent the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than a silicon-containing group; And silicon containing groups are preferred. R ⁷ and R ^{10 each} represent the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than a silicon-containing group; And silicon containing groups are preferred. R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, it is preferred that ^{R 6} and ^{R 11} are not both a hydrogen ^atom, more preferably R ^6, R ^{7, R 10} and ^{R 11} are not both a hydrogen atom, ^{R 6} and ^{R 11} is It is further preferred that R ⁷ and R ¹⁰ be the same group selected from the group consisting of a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ be the same group selected from the group consisting of a hydrocarbon group and a silicon-containing group . It is also preferred that R ⁶ and R ⁷ bond together to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ bond together to form an alicyclic or aromatic ring.

Examples of hydrocarbon group, silicon-containing group and hetero atom-containing group as R ^{5 to} R ¹² and preferable groups are hydrocarbon group (f1) and silicon-containing group (f2) and substituted group in the substituted cyclopentadienyl group, respectively. The same groups as those exemplified for the hetero atom-containing group can be mentioned.

The substituted fluorenyl group when R ⁶ and R ⁷ and R ¹⁰ and R ¹¹ combine with each other to form an alicyclic or aromatic ring is derived from the compounds represented by the formulas [II] to [VI] described later Groups are mentioned as suitable examples.

(Crosslinked part)
In formula (I), R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. The important point in the process for producing an olefin polymer is that the bridging atoms Y ^{1 in} the bridging part have R ¹³ and R ¹⁴ which are aryl groups which may be identical or different. R ¹³ and R ¹⁴ are preferably identical to each other for ease of production.

  Examples of the aryl group include a group in which one or more of a phenyl group, a naphthyl group, an anthracenyl group and aromatic hydrogens (sp2-type hydrogens) that they have are substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2) exemplified for the substituted cyclopentadienyl group, a halogen atom and a halogenated hydrocarbon group.

  Specific examples of the aryl group include unsubstituted aryl groups having 6 to 14 and preferably 6 to 10 carbon atoms such as phenyl, naphthyl, anthracenyl and biphenyl; tolyl, isopropylphenyl and n-butylphenyl Alkyl group-substituted aryl group such as t-butylphenyl group and dimethylphenyl group; cycloalkyl group-substituted aryl group such as cyclohexylphenyl group; halogenated aryl group such as chlorophenyl group, bromophenyl group, dichlorophenyl group and dibromophenyl group And halogenated alkyl group-substituted aryl groups such as (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group. The position of the substituent is preferably meta and / or para. 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 compound (A))
In the above formula (I), Q can be coordinated with 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 J 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.

  Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As a hydrocarbon group, a C1-C10 linear or branched aliphatic hydrocarbon group and a C3-C10 alicyclic hydrocarbon group are mentioned, for example. As an aliphatic hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3 -A trimethylbutyl group and neopentyl group are mentioned. As an alicyclic hydrocarbon group, a cyclohexyl group, a cyclohexylmethyl group, 1-methyl- 1-cyclohexyl group is mentioned, for example.

  As a halogenated hydrocarbon group, the group by which the at least 1 hydrogen atom which the said hydrocarbon group in Q has was substituted by the said halogen atom is mentioned.

  Specific examples of neutral conjugated or nonconjugated dienes having 4 to 10 carbon atoms include s-cis- or s-trans-.eta.4-1,3-butadiene, s-cis- or s-trans-.eta.4-1 , 4-Diphenyl-1,3-butadiene, s-cis- or s-trans-η4-3-methyl-1,3-pentadiene, s-cis- or s-trans-η4-1,4-dibenzyl-1 , 3-Butadiene, s-cis- or s-trans-η4-2,4-hexadiene, s-cis- or s-trans-η4-1,3-pentadiene, s-cis- or s-trans-η4- There may be mentioned 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

  Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand which can be coordinated by a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- 1,2- Ethers such as dimethoxyethane are mentioned.

  In formula (I), M represents a titanium atom, a zirconium atom or a hafnium atom. Among these, a hafnium atom is preferable also from the point which can copolymerize a macromonomer with high efficiency, and can be controlled to high molecular weight. In particular, in an industrial process in which polymerization is carried out under high pressure and high temperature conditions in order to ensure high productivity, it is preferable that M is a hafnium atom from the above-mentioned properties. This is because, under high pressure conditions, the abundance ratio of ethylene and α-olefin is higher than that of the macromonomer, and under high temperature conditions a decrease in molecular weight generally occurs, so the macromonomer is efficiently copolymerized as described above, This is because it is important to use a catalyst capable of controlling the polymer to a high molecular weight.

  The characteristic that such M is a hafnium atom is (1) that the Lewis acidity of the hafnium atom is smaller and the reactivity is lower than that of the zirconium atom or titanium atom, and (2) the zirconium atom or titanium atom Chain transfer reaction including β-hydrogen elimination reaction of polymerization active species which is one of the molecular weight determining factor that the bonding energy between hafnium atom and carbon atom is large compared with Is considered to be attributable to the suppression of

  Specific examples of the substituted fluorenyl group constituting the bridged metallocene compound (A) are shown in the following formulas [II] to [VI]. In the exemplified compounds of the bridged metallocene compound (A) described later, octamethyloctahydrodibenzofluorenyl represents a group derived from a compound having a structure represented by the following formula [II], and octamethyltetrahydrodicyclopenta The term "fluorenyl" refers to a group derived from a compound having a structure represented by the following formula [III], and the term "dibenzofluorenyl" refers to a group derived from a compound having a structure represented by the following formula [IV]. , 1 ′, 3, 6, 8, 8′-hexamethyl-2, 7-dihydrodicyclopentafluorenyl is a group derived from a compound having a structure represented by the following formula [V], , 3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl represents a group derived from a compound having a structure represented by the following formula [VI].

(Example of Preferred Bridged Metallocene Compound (A))
Examples of the bridged metallocene compound (A) include the following compounds.
Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1,1 ′, 3,6,8,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (2,7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- ( Dimethylphenyl) -3,6-ditert-bu Rufuruoreniru) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butyl fluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1) ', 3, 6, 8, 8'-hexamethyl-2, 7 Dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentaflu) Olenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclo) Pentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3 , 6-Di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentene) Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetra) Methylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) 1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6- Di-tert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert- Tylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (Cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) 1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6- Di-tert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert- Tylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (Cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadi) Enil) 1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1,3,3 3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (P-bromophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert- Tylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) ) Methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, di (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconiu Dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoro) Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopenta) Dienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconiu Dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoro) Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopenta) Dienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butyl fluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyl octahydrodibenzo fluorenyl) zirconium dichloride, di (p- tert-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichlori , Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8 ′ ′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, (P-tert-Butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di- p-tert-Butyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) ( 2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butyl fluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, di (p- n-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-n-butyl-pheny) ) Methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) Methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7- Dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadie) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (2) Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylful) Orenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,1) ', 3, 6, 8, 8 '-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3', 6,6 ', 8-hexamethyl-2 7,7-Dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride (P-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2, 7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichlori Di (p-biphenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (Enyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (1-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1) ', 3, 6, 8, 8'- hexame 2,7-Dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3,3 ′, 6,6 ′, 8-hexamethyl-2,7 -Dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1 -Naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,3 6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,1) ', 3, 6, 8, 8'- hexame 2,7-Dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3,3 ', 6,6', 8-hexamethyl-2,7 -Dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2 -Naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,3 6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluore) Nil) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl ) Zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3 , 6-di-tert-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,1 ′, 3,6,8,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) Zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) ) (2,7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- ( Dimethylphenyl) -3,6-ditert-bu Rufuruoreniru) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butyl fluorenyl) zirconium dichloride.

  Further, as the bridged metallocene compound (A), a compound obtained by changing “zirconium” in the above-mentioned exemplified compounds to “hafnium” or “titanium”, “dichloride” “difluoride”, “dibromide”, “diaiodide”, “dimethyl” “Cyclopentadienyl” is converted to “3-tert-butyl-5-methyl-cyclopentadienyl”, “3,5-dimethyl-cyclopentadiyl”, “methyl ethyl” or “dibenzyl”, etc. Mention may also be made of compounds which have been changed to, for example, enil, "3-tert-butyl-cyclopentadienyl" or "3-methyl-cyclopentadienyl".

  The bridged metallocene compound (A) can be produced by a known method. Examples of known methods include the methods described in WO 01/27124 and WO 04/029062. Moreover, the said bridge | crosslinking metallocene compound (A) can be used individually by 1 type or in combination of 2 or more types.

(Transition metal compound (B))
The transition metal compound (B) used in the present invention is a compound having a structure represented by the following formula [B], and functions as a catalyst for olefin polymerization in the presence of a compound (C) described later.

(In the formula [B],
M represents a transition metal atom of Group 4 or 5 of the periodic table.
m is an integer of 1 to 4;
R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms represented by the general formula C _{n ′} H _{2 n ′ + 1} (n ′ is an integer of 1 to 8).
R ^{2 to} R ⁵ each independently represent 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, a phosphorus containing group, a silicon containing A group, a germanium-containing group, or a tin-containing group is shown, and two or more of these may be bonded to each other to form a ring.
R ^{6 to} R ^{8 each} represent a hydrocarbon group, at least one of which is an aromatic hydrocarbon group, and when m is an integer of 2 or more, R may be R between structural units of the formula [B] ^Two groups among the groups represented by ^{2 to} R ⁸ may be linked.
n is a number satisfying the valence of M, 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, And X represents 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, plural Xs may be the same or different. In addition, a plurality of groups represented by X may be bonded to each other to form a ring. )

  The olefin polymerization catalyst containing the transition metal compound (B) generates a vinyl-terminated macromonomer which is an ethylene polymer, and plays a role of generating a site forming a side chain of the olefin polymer [R1]. That is, the olefin polymerization catalyst containing the transition metal compound (B) has a feature of mainly polymerizing ethylene to form an ethylene polymer which becomes a vinyl group at one terminal with high selectivity. Furthermore, the olefin polymerization catalyst containing the transition metal compound (B) is characterized by producing a relatively low molecular weight ethylene polymer (weight average molecular weight is in the range of 200 to 10,000). Since the olefin polymerization catalyst containing the transition metal compound (B) has the above-mentioned features, side chains are efficiently introduced into the olefin polymer [R1], and the propylene resin composition of the present invention The surface hardness is high, and the physical property balance between impact resistance and rigidity is excellent.

  Furthermore, the olefin polymerization catalyst containing the transition metal compound (B) has a feature of polymerizing ethylene with high selectivity even under the condition where ethylene coexists with an α-olefin and a vinyl-terminated macromonomer. The side chain of the olefin polymer [R1] well retains the mechanical properties and thermal properties as an ethylene polymer, and the propylene resin composition of the present invention has high surface hardness, impact resistance and rigidity. It becomes an excellent balance of physical properties. Moreover, the said characteristic is a preferable characteristic also in employ | adopting polymerization method [b] among the manufacturing methods mentioned later. Further, the catalyst for olefin polymerization containing the transition metal compound (B) is preferable from the viewpoint of light resistance, color resistance and the like because it has an ability not to substantially generate an olefin structure, so-called internal olefin inside the polymer chain. Hereinafter, features of the chemical structure of the transition metal compound (B) used in the present invention will be described.

  In the above Formula [B], N... M generally indicates coordination, but in the present invention it may or may not be coordination.

  In Formula [B], M represents a transition metal atom of Group 4 or 5 of the periodic table, and specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum or the like. It is preferably a metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium, more preferably zirconium.

  m is an integer of 1 to 4, preferably 1 to 2, and more preferably 2.

R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms represented by the general formula C _{n ′} H _{2 n ′ + 1} (n ′ is an integer of 1 to 8), and specifically, a methyl group or ethyl group Acyclic hydrocarbon group such as n-propyl group, n-butyl group, iso-propyl group, iso-butyl group, tert-butyl group, neopentyl group, n-hexyl group; cyclopropyl group, cyclobutyl group, And cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl. Preferably, it is a linear hydrocarbon group, and specifically, a methyl group, an ethyl group, an n-propyl group or an n-butyl group. Among these, methyl, ethyl and n-propyl are more preferable, and methyl and ethyl are more preferable. By selecting the above-mentioned hydrocarbon group, an ethylene polymer having a relatively low molecular weight, for example, a weight average molecular weight within the range of 200 to 10,000 can be produced, and as described above, the propylene of the present invention It becomes easy to obtain a system resin composition.

R ^{2 to} R ⁵ each independently represent 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, a phosphorus containing group, a silicon containing A group, a germanium containing group, or a tin containing group is shown. R ^{2 to} R ⁵ each represent an alicyclic ring, an aromatic ring or a ring such as a hydrocarbon ring containing a hetero atom such as a nitrogen atom when two or more of these groups, preferably adjacent groups, are bonded to each other These rings may be formed, and these rings may further have a substituent.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  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, n-hexyl group and the like. A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms; a linear or branched alkyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as a vinyl group, an allyl group or an isopropenyl group Or branched alkenyl group; linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl group and propargyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms, such as a cyclopentadienyl group, an indenyl group, Group having 5 to 30 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like, having 6 to 30, preferably 6 to 20 carbon atoms. And aryl groups; alkyl substituted aryl groups such as tolyl group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group, and di-t-butylphenyl group.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen, and for example, a halogenated carbon having 1 to 30, preferably 1 to 20 carbon atoms such as trifluoromethyl group, pentafluorophenyl group, chlorophenyl group and the like A hydrogen group is mentioned. The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as benzyl group and cumyl group.

  The hydrocarbon group is a heterocyclic compound residue; oxygen such as alkoxy group, aryloxy group, ether group, ether group, acyl group, ester group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic acid anhydride group, etc. Containing group: amino group, imino group, amido group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, nitro group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group with ammonium salt Nitrogen-containing groups such as: boranediyl group, boranetriyl group, boron-containing group such as diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, Isothiocyanic acid ester group, sulfone ester group, sulfo Sulfur-containing groups such as amide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group and sulfenyl group; phosphorus-containing groups such as phosphido group, phosphoryl group, thiophosphoryl group and phosphato group, silicon-containing group It may further have a substituent such as a germanium-containing group or a tin-containing group.

  Among these, as the above-mentioned hydrocarbon group, 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 And the like, and linear and branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; and 6 to 6 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. 30, preferably 6 to 20 aryl groups; wherein the aryl group contains a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or an alkoxy group, 6 to 30 carbon atoms, preferably 6 to 20 And substituted aryl groups in which 1 to 5 substituents such as aryloxy groups are substituted.

  As a heterocyclic compound residue, a nitrogen-containing compound such as pyrrole, pyridine, pyrimidine, quinoline or triazine, an oxygen-containing compound such as furan or pyran, a residue such as a sulfur-containing compound such as thiophene, and the like The compound residue may, for example, be a group further substituted by a substituent such as an alkyl group having 1 to 30, preferably 1 to 20 carbon atoms, or an alkoxy group. Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group include the same as those exemplified as the substituent which the above-mentioned hydrocarbon group may have.

  Specific examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, etc. Specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group And diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable, and trimethylsilyl, triethylsilyl and triphenylsilyl are preferable. And dimethylphenylsilyl are more preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group and the like. As a germanium containing group and a tin containing group, what substituted the silicon of the said silicon containing group by germanium and tin is mentioned.

Next, the substituent which the said hydrocarbon group as R < ² > -R < ⁵ > mentioned above may have is demonstrated more concretely. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group and the like. Specific examples of the aryloxy group include phenoxy group, 2,6-dimethylphenoxy group and 2,4,6-trimethylphenoxy group.

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

  Specific examples of the amino group include dimethylamino, ethylmethylamino and diphenylamino. 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 amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specifically as an imido group, an aceto imide group, a benz imide group, etc. are mentioned.

  Specific examples of the thioester group include acetylthio group, benzoylthio group, methylthiocarbonyl group and phenylthiocarbonyl group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the arylthio group include phenylthio group, methylphenylthio group and naphthylthio group.

  Specific examples of sulfone ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate groups. Specific examples of the sulfonamide group include phenyl sulfonamide group, N-methyl sulfonamide group, N-methyl-p-toluene sulfonamide group and the like.

  n is a number satisfying the valence number of M, and is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3. X represents 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 A group, a germanium containing group, or a tin containing group is shown. In addition, when n is 2 or more, several groups shown by X may mutually be same or different. Also, a plurality of groups represented by X may be bonded to each other to form a ring.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include the same groups as those exemplified by the R ² to R ^5. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group and icosyl group; carbons such as cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group Cycloalkyl group having 3 to 30 atoms; alkenyl group such as vinyl group, propenyl group and cyclohexenyl group; arylalkyl group such as benzyl group, phenylethyl group and phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, Examples thereof include, but not limited to, aryl groups such as trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, and the like. Moreover, these hydrocarbon groups may be groups obtained by substituting at least one hydrogen atom of a halogenated hydrocarbon, specifically, a hydrocarbon group having 1 to 20 carbon atoms with a halogen atom. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable.

Examples of the oxygen-containing group include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ , and specific examples thereof include a hydroxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; And aryloxy groups such as methyl phenoxy group, dimethyl phenoxy group and naphthoxy group; aryl alkoxy groups such as phenyl methoxy group and phenyl ethoxy group; acetoxy group; carbonyl group etc., but it is not limited thereto.

Examples of the sulfur-containing group include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ , and more specifically, methylsulfonate group, trifluoromethanesulfonate group, phenylsulfonate group, benzylsulfonate group, p-toluenesulfonate Sulfonate groups such as trimethylbenzene sulfonate group, triisobutylbenzene sulfonate group, p-chlorobenzene sulfonate group, pentafluorobenzene sulfonate group, etc .; methylsulfinate group, phenylsulfinate group, benzylsulfinate group, p- Sulfinate groups such as toluene sulfinate group, trimethylbenzene sulfinate group, pentafluorobenzene sulfinate group and the like; alkylthio groups; arylthio groups and the like, but not limited thereto .

Examples of the nitrogen-containing group include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ , and specific examples thereof include an amino group; a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, and dibutylamino. And alkylamino groups such as dicyclohexylamino group; phenylamino groups, diphenylamino groups, ditolylamino groups, dinaphthylamino groups, arylamino groups such as methylphenylamino groups and alkylarylamino groups; It is not something to be done.

Specific examples of the boron-containing group include BR ₄ (R represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like). Specific examples of the aluminum-containing group include AlR ₄ (R represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like), but is not limited thereto. . 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 tolylylphosphine group; methyl phosphite group, ethyl Examples thereof include, but are not limited to, phosphite groups, and phosphite groups such as phenyl phosphite groups (phosphido groups); phosphonic acid groups; phosphinic acid groups and the like.

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. Examples of the heterocyclic compound residue include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ .

Specific examples of the silicon-containing group include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ , and specific examples thereof include a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group and a tripropylsilyl group. -Substituted hydrocarbon such as tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; hydrocarbon-substituted silyl groups such as trimethylsilyl ether; trimethylsilylmethyl and the like Silicon-substituted alkyl groups; silicon-substituted aryl groups such as trimethylsilylphenyl group and the like. Specifically as a germanium containing group, the thing similar to what was illustrated by said R < ² > -R < ⁵ > is mentioned, The group which substituted silicon of the said silicon containing group to germanium is mentioned specifically ,. Specific examples of the tin-containing group include the same as those exemplified for the aforementioned R ^{2 to} R ⁵ , and more specifically, a group in which silicon of the silicon-containing group is substituted with tin.

R ^{6 to} R ⁸ are hydrocarbon groups, at least one of which is an aromatic hydrocarbon group. 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, n-hexyl group and the like. Of 1 to 30 carbon atoms, preferably 1 to 20 linear or branched alkyl groups; and 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl. And branched alkenyl groups; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms, such as adamantyl group; cyclopentadienyl group, indenyl group, fluorene Cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as alkyl group; 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group and the like And aryl substituted groups such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl.

  The hydrogen atom of the hydrocarbon group may be substituted with a halogen atom, and as such a hydrocarbon group, for example, 1 to 30 carbon atoms such as trifluoromethyl group, pentafluorophenyl group, chlorophenyl group and the like Preferably, 1 to 20 halogenated hydrocarbon groups can be mentioned. The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as a benzyl group and a cumyl group.

  Specific examples of the aromatic hydrocarbon group include aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl groups; And alkyl substituted aryl groups such as isopropylphenyl group, t-butylphenyl group, dimethylphenyl group and di-t-butylphenyl group. In the aromatic hydrocarbon group, a hydrogen atom may be substituted by a halogen atom, or may be substituted by another hydrocarbon group.

Since at least one of the hydrocarbon groups of R ^{6 to} R ⁸ is an aromatic hydrocarbon group, the polymerization catalyst containing the transition metal compound (B) gives good activity even under high temperature polymerization conditions, The propylene-based resin composition of the present invention is suitable for producing the olefin-based resin (β) according to the present invention, and exhibits good performance.

When m is an integer of 2 or more, two groups among the groups represented by R ^{2 to} R ⁸ may be connected between the structural units of the formula [B]. Furthermore, when m is an integer of 2 or more, R ^1's , R ^{2 's} , R ^{3' s} , R ^{4 's} , R ^{5' s} , R ^{6 's} , R ^{7' s} , R ^{8 's} are identical to or different from each other It may be

  The transition metal compounds (B) represented by the formula [B] as described above can be used singly or in combination of two or more.

(Compound (C))
The compound (C) used in the present invention reacts with the bridged metallocene compound (A) and the transition metal compound (B) to function as a catalyst for olefin polymerization, and specifically, (C-1) It is selected from the group consisting of an organometallic compound, (C-2) organoaluminum oxy compound, and (C-3) a bridged metallocene compound (A) or a compound which reacts with a transition metal compound (B) to form an ion pair . With respect to such compounds (C-1) to (C-3), the compounds (C-1) to (C-3) described in WO 2015/147186 can be used as it is without limitation. In Examples to be described later, triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate are used, but the present invention is not limited to these compounds.

  Hereinafter, a method of polymerizing an olefin in the presence of a catalyst for olefin polymerization including the compounds (A), (B) and (C) to produce an olefin resin (β) will be described.

  The polymerization can be carried out by any of solution polymerization method, bulk polymerization method, liquid phase polymerization method such as suspension polymerization, and gas phase polymerization method, but the latter step [a-2] and polymerization of polymerization method [a] described later Method [b] is carried out by a liquid phase polymerization method.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like or mixtures thereof. Moreover, the olefin itself to be polymerized can also be used as a solvent.

In the case of using a catalyst for olefin polymerization containing the compounds (A), (B) and (C) in the production of the olefin resin (β), the crosslinked metallocene compound (A) is generally 10 ⁻⁸ per liter of reaction volume. to 1 mol, preferably used in an amount of ¹⁰ -7 to 0.5 mole, the transition metal compound (B), reaction volume per liter, usually ¹⁰ -12 ^{to 10 -2} mol, preferably ^{10 -10} It is used in an amount of -10 ^-3 mol. In the bridged metallocene compound (A) and the transition metal compound (B), the molar ratio (B / A) of the transition metal compound (B) to the bridged metallocene compound (A) is usually 0.00001 to 100, preferably It is used in an amount of 0.00005-10, more preferably 0.0001-5.

  The organometallic compound (C-1) includes the organometallic compound (C-1), the bridged metallocene compound (A) and the transition metal atom (M) in the transition metal compound (B) (in the bridged metallocene compound (A) The molar ratio (C-1 / M) to the titanium atom, zirconium atom or hafnium atom) is usually 0.01 to 100,000, preferably 0.05 to 50,000.

  The organoaluminum oxy compound (C-2) is a transition metal atom (M) in the bridged metallocene compound (A) and the transition metal compound (B) of the aluminum atom in the organoaluminum oxy compound (C-2) (bridged metallocene In the compound (A), the molar ratio (C-2 / M) to the titanium atom, zirconium atom or hafnium atom) is usually 10 to 500,000, preferably 20 to 100,000.

  The ionizing ionic compound (C-3) is a transition metal atom (M) in the bridged metallocene compound (A) and the transition metal compound (B) of the ionizing ionic compound (C-3) (bridged metallocene compound (A) In (1), the molar ratio (C-3 / M) to the titanium atom, zirconium atom or hafnium atom) is usually 1 to 10, preferably 1 to 5.

Moreover, the polymerization temperature of the olefin using such a catalyst for olefin polymerization is usually in the range of -50 to + 300 ° C, preferably 0 to 170 ° C. The polymerization pressure is usually normal pressure to 9.8 MPa (100 kg / cm ² ), preferably normal pressure to 4.9 MPa (50 kg / cm ² ), and the polymerization reaction is batchwise, semi-continuous or continuous. It can be performed by any method.

  The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by varying the polymerization temperature. Furthermore, it can also be adjusted by selection of the compound of any of the compounds (A), (B) and (C) to be used, or selection of the combination.

  As an olefin used for superposition | polymerization, ethylene and the C3-C20 alpha olefin mentioned above are mentioned. These olefins can be used in combination of ethylene as an essential monomer and one or more other monomers.

In the present invention, the olefin resin (β) can be produced by any of the following polymerization method [a] or polymerization method [b].
・ Polymerization method [a]
In the presence of the reaction product of the previous step [a-1] and then the previous step [a-1] to obtain ethylene-terminated macromonomer by polymerizing ethylene in the presence of the transition metal compound (B) and the compound (C) After copolymerizing ethylene and at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms in the presence of the bridged metallocene compound (A) and the compound (C) a-2].
・ Polymerization method [b]
In the presence of a bridged metallocene compound (A), a transition metal compound (B) and a compound (C), ethylene and at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms To copolymerize.
Hereinafter, preferred embodiments of the polymerization method [a] and the polymerization method [b] will be described.

・ Polymerization method [a]
(Preceding process [a-1])
In this step, ethylene is mainly polymerized by the olefin polymerization catalyst comprising the transition metal compound (B) and the compound (C) to obtain a vinyl-terminated macromonomer which is substantially an ethylene polymer, and the polymerization method is in the above-mentioned range There is no particular restriction. In the case of liquid phase polymerization, the resulting reaction solution may be introduced as it is into the subsequent step, or after taking out the vinyl-terminated macromonomer, the vinyl-terminated macromonomer may be introduced into the subsequent step as a block or powder. It may be introduced as a slurry or as a re-dissolution into a subsequent step.

(Post process [a-2])
And at least one α-olefin selected from the group consisting of ethylene and α-olefins of 3 to 20 carbon atoms in the presence of the bridged metallocene compound (A) and the compound (C), and the previous step [a-1 And the subsequent step of copolymerizing with the vinyl-terminated macromonomer obtained in The polymerization method is not particularly limited in the above-mentioned range, but a liquid phase polymerization method is preferable since it is a step of forming an amorphous or low crystalline ethylene / α-olefin copolymer site, and in particular each monomer concentration The solution polymerization method is preferable in order to obtain the olefin resin (β) having a desired structure by controlling

  The polymerization reaction may be carried out batchwise both in the pre-step [a-1] and the post-step [a-2], and the pre-step [a-1] is carried out batchwise, and the removed vinyl-terminated macromonomer is introduced. By carrying out, the post process [a-2] may be performed in a continuous manner. Furthermore, a back process [a-2] can also be performed by a continuous type by performing a front process [a-1] by a continuous type and introduce | transducing a product as it is. Moreover, pre-process [a-1] can be performed by a continuous type, and post-process [a-2] can also be performed by a batch system.

・ Polymerization method [b]
In the presence of a bridged metallocene compound (A), a transition metal compound (B) and a compound (C), ethylene and at least one α-olefin selected from the group consisting of α-olefins of 3 to 20 carbon atoms Can be carried out in one polymerization vessel. The catalyst for olefin polymerization comprising the transition metal compound (B) and the compound (C) tends to polymerize ethylene highly selectively even if an α-olefin other than ethylene is present in the polymerization system. Furthermore, the catalyst tends to produce relatively low molecular weight polymers, and the resulting polymers have vinyl ends. Therefore, the catalyst for olefin polymerization which consists of a transition metal compound (B) and a compound (C) can produce the vinyl terminal macromonomer which is an ethylene polymer substantially.

  On the other hand, a catalyst for olefin polymerization comprising a bridged metallocene compound (A) and a compound (C) can produce a polymer having a large molecular weight, and ethylene, α-olefin, transition metal compound (B), compound ( The resulting vinyl-terminated macromonomer can be copolymerized using an olefin polymerization catalyst consisting of C). Thus, the olefin polymer [R1] can be contained in the olefin resin (β) under one polymerization reaction condition.

  In the method for producing an olefin resin (β), the post-step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] are carried out by solution polymerization in a temperature range of 80 to 300 ° C. Is preferred.

  In addition, a "solution polymerization method" is a general term for the method of superposing | polymerizing in the state which used the said inactive hydrocarbon as a polymerization solvent and the polymer melt | dissolved. Examples of the polymerization solvent used in the post-step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, toluene and xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and these can be used singly or in combination of two or more. Among these, from the industrial viewpoint, aliphatic hydrocarbons such as hexane and heptane are preferable, and hexane is more preferable from the viewpoint of separation with an olefin resin (β) and purification.

  Moreover, the range of 80-200 degreeC is preferable, and, as for the polymerization temperature of the superposition | polymerization process of post-process [a-2] of superposition | polymerization method [a] and superposition | polymerization method [b], the range of 90-200 degreeC is more preferable. Such a temperature is preferable because the temperature at which the vinyl-terminated macromonomer dissolves well in an aliphatic hydrocarbon such as hexane or heptane that is preferably used industrially as the polymerization solvent is 90 ° C. or higher. . The polymerization temperature is preferably higher to improve the introduction efficiency of the polyethylene side chain. Furthermore, from the viewpoint of improving productivity, the polymerization temperature is preferably higher.

  The polymerization pressure in the polymerization step of the polymerization step [a-2] and the polymerization step of the polymerization method [b] is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, more preferably atmospheric pressure It is the conditions of -3MPa gauge pressure. Furthermore, it is preferable that it is a 0.5-3 MPa gauge pressure from a viewpoint of a productivity improvement.

  The polymerization reaction can be carried out either batchwise, semicontinuously or continuously. Furthermore, it is also possible to divide the polymerization into two or more stages under different reaction conditions. In the present invention, among these, it is preferable to adopt a method of continuously supplying monomers to the reactor to carry out copolymerization.

  Reaction time (average residence time when copolymerization is carried out in a continuous process) of the polymerization step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] is the catalyst concentration, polymerization temperature, etc. Although it changes also with conditions of 5, it is normally 0.5 minute-5 hours, Preferably 5 minutes-3 hours.

  The polymer concentration in the post-process [a-2] of the polymerization method [a] and the polymerization method [b] is usually 5 to 50% by mass, preferably 10 to 40% by mass at the time of steady operation. The polymer concentration is preferably 15 to 35% by mass from the viewpoint of viscosity limitation in polymerization ability, post-processing step (desolvation) loading and productivity.

  The molecular weight of the resulting olefin polymer can also be adjusted within the range by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (C) used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 NL per kg of the olefin polymer to be produced.

<Propylene-based resin composition>
The propylene-based resin composition of the present invention contains a propylene-based polymer (α) and an olefin-based resin (β). In the propylene-based resin composition of the present invention, the inorganic filler is added to 100 parts by mass of α and β, with 100 parts by mass as the total of the propylene-based polymer (α) and the olefin-based resin (β). The propylene polymer (α) is 70 to 80 parts by mass, preferably 72 to 77 parts by mass, and more preferably 73 to 75 parts by mass The olefin resin (β) is more than 20 parts by mass and 30 parts by mass or less, preferably 23 parts by mass or more and 28 parts by mass or less, more preferably 25 parts by mass or more and 27 parts by mass or less. When the content of the propylene-based polymer (α) and the olefin-based resin (β) is within the above range, the balance between low-temperature impact resistance and hardness is good without lowering the rigidity of the propylene-based resin composition And can be suitably used for various molded articles.

  Furthermore, in the propylene-based resin composition according to the present invention, resins other than the essential components of the propylene-based polymer (α) and the olefin-based resin (β), as long as the object of the present invention is not impaired Rubber, inorganic filler, organic filler, etc., and also weather resistant stabilizer, heat resistant stabilizer, antistatic agent, antislip agent, anti blocking agent, antifogging agent, lubricant, pigment, dye, Additives such as plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, nucleating agents, etc. can be blended. In the propylene-based resin composition according to the present invention, the addition amount of the other resin, the other rubber, the inorganic filler, the additive and the like is particularly limited as long as the object of the present invention is not impaired. is not.

  The flexural modulus (FM) of the propylene-based resin composition of the present invention measured according to JIS K7171 is in the range of 600 to 2500 MPa, preferably 900 to 2300 MPa, and more preferably in the range of 1300 to 2200 MPa. It is. Molded articles using a low-rigidity propylene-based resin composition having a flexural modulus of less than 600 MPa have poor practical rigidity, and when the flexural modulus exceeds 2500 MPa, the formability is poor or the molded article becomes brittle. May be

  The tensile modulus of elasticity of the propylene-based resin composition of the present invention measured in accordance with ISO 527-2 is preferably in the range of 400 to 2300 MPa, more preferably 110 to 2000 MPa. If the tensile elastic modulus is within the above range, it is excellent in the balance of practical rigidity, impact property and moldability.

  The preparation method of the propylene-based resin composition in the present invention is not particularly limited, such as a melting method and a solution method, but a melt-kneading method is preferable practically. As the melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. For example, after uniformly mixing powdery or granular components together with optional components such as the above-mentioned additives if necessary using a Henschel mixer, ribbon blender, V-type blender or the like, a uniaxial or multiaxial kneading extruder It can be prepared by kneading with a kneading roll, a batch kneader, a kneader, a Banbury mixer or the like.

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

<Molded body>
The propylene-based resin composition according to the present invention can improve the impact resistance while maintaining the rigidity, and is excellent in the balance between the rigidity and the impact resistance, so injection molding, extrusion molding, inflation molding, blow molding It can be molded into various molded articles by known molding methods such as molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding and the like. The molded article can be applied to various known applications such as automotive parts, containers for food and medical applications, and packaging materials for food and electronic materials. In addition, the molded article can be applied to films, sheets, tapes, and other uses.

  The molded article using the propylene-based resin composition according to the present invention is excellent in the balance between rigidity and impact resistance, has high surface hardness, and is excellent in chemical resistance, and can be used for various automobile parts. The molded body is, for example, automobile exterior parts such as bumpers, side moldings, aerodynamic undercovers, automobile interior parts such as instrument panels and interior trims, fenders, door panels, outer plate parts such as steps, engine covers, fans, fans It can be used for engine peripheral parts such as the Cheroid.

Containers for food use and medical use, for example, dishes, retort containers, frozen storage containers, retort pouches, microwave heat resistant containers, frozen food containers, frozen food containers, food containers such as 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 bottles, medicine 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, freshness Holding film, pharmaceutical packaging material, cell culture bag, cell inspection film, bulb packaging material, seed packaging material, film for vegetable and mushroom cultivation, heat-resistant vacuum formed container, sugar container, lid for sugar beet, commercial wrap film, household use Wrap film, baking carton, etc. may be mentioned.

  Films, sheets and tapes include, for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electric parts and appliances, protective films for mobile phones, for personal computers Protective films, such as a protective film, a masking film, a film for condensers, a reflective film, a laminate (including glass), a radiation resistant film, a gamma ray resistant film, a porous film and the like can be mentioned.

  Other applications include, for example, casings of household electric appliances, hoses, tubes, wire coating materials, insulators for high-voltage wires, tubes for cosmetics and perfume sprays, tubes for medical use, infusion tubes, pipes, wire harnesses, motorcycles and railways. Vehicle / aircraft / ship interior materials, instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, arm box, armrest, airbag case lid, shift knob, assist grip, side step Mats, reclining covers, seats in trunks, seat belt buckles, molding materials such as inner and outer moldings, roof moldings, belt moldings, door seals, automotive sealing materials such as body seals, glass run channels, mudguards, Automotive interior / exterior materials such as cooking plates, step mats, license plate housings, automotive hose members, air duct hoses, air duct covers, air intake pipes, air dam pipes, timing belt cover seals, bonnet cushions, door cushions, damping tires, Special tires such as static tire, car race tire, radio control tire, packing, car dust cover, lamp seal, car boot material, rack and pinion boot, timing belt, wire harness, grommet, emblem, air filter packing, furniture, Footwear, clothing, bags, building materials, skin materials, sealing materials for buildings, waterproof sheets, building materials, gaskets, window films for building materials, window films for core materials, iron core protection members, gaskets, doors, door frames, window frames, rims Baseboards, opening frames, etc. Flooring materials, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, anti-fall films / mats / sheets), health appliance parts, shock absorbing pads, protectors / protections (eg : Helmets, guards, sporting goods (eg sport grips, protectors), sports equipment, rackets, mouth guards, balls, golf balls, transport tools (eg transport shock absorbing grips, shock absorbing sheets), damping Pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, shock absorbing materials such as shock absorbing films, grip materials, miscellaneous goods, toys, soles, soles, soles for shoes, midsoles / insoles for shoes, Sole, sandal, suction cup, toothbrush, floor material, mat for gymnastics, electric tool member, agricultural machine member, heat dissipating material, transparent substrate, soundproofing material, cushion Materials, electric cables, shape memory materials, medical gaskets, medical caps, medicine caps, stoppers, gaskets, baby food, dairy products, medicines, sterile water, etc. are filled in a bottle and then subjected to high temperature treatment such as boiling or high pressure steam sterilization Packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, fax legs, sewing machine legs, motor support mats, audio protection Precision equipment such as vibration material / OA equipment support member, heat resistant packing for OA, animal cage, beaker, physicochemical equipment such as beaker, measuring cylinder, cell for optical measurement, costume case, clear case, clear file, clear sheet, desk mat, As the use as a fiber, for example, non-woven fabric, non-stretchable Fabrics, fibers, tarpaulins, breathable fabric or cloth, disposable diapers, sanitary goods, sanitary goods, a filter, a bag filter, dust collection filter, air cleaner, the hollow fiber filter, water filters, and the like gas separation membrane.

  Among these, molded articles obtained from the propylene-based resin composition of the present invention can improve impact resistance while maintaining rigidity, and are excellent in balance of rigidity, impact resistance and hardness, In particular, it can be suitably used for automobile interior and exterior materials such as bumpers and instrument panels, outer plate materials, food containers, and beverage containers.

  EXAMPLES The present invention will be more specifically described by way of the following examples, but the present invention is not limited to these examples as long as the gist of the invention is not exceeded. In the following examples, physical properties of the olefin resin (β), the propylene polymer (α) and the propylene resin composition were measured by the following methods.

<Method of measuring physical properties of olefin resin (β)>
(1) Melting temperature (Tm) and heat of melting ΔH
The melting temperature (Tm) and the heat of fusion ΔH were determined by DSC measurement under the following conditions.
Using a differential scanning calorimeter (trade name: RDC 220, manufactured by Seiko Instruments Inc.), raise approximately 10 mg of the sample from 30 ° C to 200 ° C at a heating rate of 50 ° C / min under a nitrogen atmosphere, Hold at 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 raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed at the second temperature rise was regarded as a melting peak, and the temperature at which the melting peak appeared was determined as a melting temperature (Tm). The heat of fusion ΔH was determined by calculating the area of the melting peak. In addition, when a melting peak was multimodal, it calculated and calculated | required the area of the whole melting peak.

(2) Glass transition temperature (Tg)
The glass transition temperature (Tg) was determined by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter (trade name: RDC 220, manufactured by Seiko Instruments Inc.), raise approximately 10 mg of the sample from 30 ° C to 200 ° C at a heating rate of 50 ° C / min under a nitrogen atmosphere, Hold at temperature for 10 minutes. Furthermore, it cooled to -100 degreeC with temperature-fall rate 10 degreeC / min, and after hold | maintaining for 5 minutes at the temperature, it heated up to 200 degreeC with the temperature increase rate of 10 degree-C / min. The glass transition temperature (Tg) is sensed as a change in specific heat causes the DSC curve to be bent and the baseline to be translated at the second temperature rise. The temperature at the intersection of the tangent of the baseline lower than this bending and the tangent of the point at which the slope is maximum at the bent portion was taken as the glass transition temperature (Tg).

(3) Ratio E of ortho-dichlorobenzene soluble components
The proportion E (mass%) of ortho-dichlorobenzene soluble components at 20 ° C. or less was determined by CFC measurement under the following conditions.
Equipment: Cross-fractionation chromatography CFC2 (Polymer ChAR)
Detector (built-in): Infrared spectrophotometer IR ⁴ (Polymer ChAR)
Detection wavelength: 3.42 μm (2,920 cm ^-1 ); fixed sample concentration: 120 mg / 30 mL
Injection volume: 0.5mL
Cooling time: 1.0 ° C / min Elution division: 4.0 ° C interval (−20 to 140 ° C)
GPC column: Shodex HT-806 M × 3 (trade name, manufactured by Showa Denko KK)
GPC column temperature: 140 ° C.
GPC column calibration: monodispersed polystyrene (manufactured by Tosoh Corporation)
Molecular weight calibration method: General-purpose calibration method (polystyrene conversion)
Mobile phase: ortho-dichlorobenzene (BHT added)
Flow rate: 1.0 mL / min

(4) Elastic modulus (tensile test)
The elastic modulus was calculated by measuring a test piece obtained by press-molding an olefin resin (β) at 200 ° C. for 5 minutes in accordance with ASTM D638.

(5) ¹³ C-NMR
In order to confirm the compositional analysis of the polymer α-olefin, the number of methyl branches of the macromonomer and the graft structure, ¹³ C-NMR measurement was performed under the following conditions.
Device: AVANCE III 500 CryoProbe Prodigy nuclear magnetic resonance device (trade name, manufactured by Bruker Biospin Ltd.)
Measurement kernel: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 μs)
Number of points: 64k
Measuring range: 250 ppm (-55 to 195 ppm)
Repeating time: 5.5 seconds Integration number: 512 times Measuring solvent: ortho-dichlorobenzene / 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)

(6) GPC Analysis In order to analyze the weight average molecular weight of the polymer and estimate the amount of remaining macromonomer, GPC analysis was performed under the following conditions.
Equipment: Alliance GPC 2000 type (trade name, manufactured by Waters)
Column: Two TSKgel GMH6-HTs, two TSKgel GMH6-HTLs (trade names, both manufactured by Tosoh Corp., inner diameter 7.5 mm, length 30 cm)
Column temperature: 140 ° C
Mobile phase: ortho-dichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: Differential refractometer Flow rate: 1.0 mL / min Sample concentration: 0.15% (w / v)
Injection volume: 0.5mL
Sampling time interval: 1 second Column calibration: Monodispersed polystyrene (made by Tosoh Corp.)

(7) Intrinsic viscosity ([η])
Intrinsic viscosity was measured at 135 ° C. using decalin solvent.

(8) Melt flow rate (MFR)
Melt flow rate was measured at 2.16 kg load according to ASTM D1238E. The measurement temperature was 190 ° C.

(9) Composition ratio of olefin polymer [R1] The composition ratio (% by mass) of the olefin polymer [R1] is 20% or less with the remaining macromonomer composition ratio (% by mass) calculated from GPC analysis. Estimated by subtracting the composition ratio (% by mass) of ethylene / α-olefin copolymer having no side chain estimated from the proportion E (% by mass) of ortho-dichlorobenzene soluble components in 100% by mass did.

<Method of measuring physical properties of propylene-based polymer (α)>
(10) Melt flow rate (MFR)
Melt flow rate was measured at 2.16 kg load according to ASTM D1238E. The measurement temperature was 230 ° C.

(11) Pentad fraction (mm mm)
The pentad fraction (mm mm (%)), which is one of the indices of polymer stereoregularity and whose microtacticity was examined, is shown in Macromolecules, 8, 687 (1975) for propylene-based polymer (α). It calculated from the peak intensity ratio of the < ¹³ > C-NMR spectrum assigned based on it. ^{The 13} C-NMR spectrum was measured using an apparatus of EX-400 (trade name, manufactured by Nippon Denshi Co., Ltd.) with reference to TMS, using an ortho-dichlorobenzene solvent at a temperature of 130 ° C.

<Method of measuring physical properties of propylene-based resin compositions 1, 2, C1 and C2>
The melt flow rate (MFR) was measured by the same method as (10) above.

(12) Flexural modulus The flexural modulus FM (MPa) according to JIS K7171 was calculated from the following tensile modulus.

(13) Tensile modulus of elasticity The tensile modulus of elasticity (MPa) was measured according to ISO 527-2 under the following conditions.
Test specimen: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Tensile speed: 1 mm / min Bending span: 64 mm

(14) Charpy impact value The Charpy impact value (kJ / m ² ) was measured according to ISO 179 under the following conditions.
Temperature: -30 ° C
Test specimen: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
The notches are machined.

(15) Rockwell Hardness The Rockwell hardness (R scale) was measured according to ISO 2039-2 under the following conditions.
Test specimen: 10 mm (width) x 4 mm (thickness) x 80 mm (length)

(16) Thermal deformation temperature (HDT)
The heat distortion temperature was measured in accordance with ISO 75-1, 2.

(17) High-speed surface impact strength (HRIT)
The high-speed surface impact strength was measured for total breaking energy under the following conditions.
Temperature: -30 ° C
Test specimen: 120 mm (width) × 130 mm (length) × 3.0 mm (thickness) (square plate)
Speed: 3 m / s
Shooting core: 1/2 inch φ
Receiving stand: 3 inches φ

(18) Specular glossiness The specular glossiness (60 °) was measured in accordance with JIS Z8741.

(19) Scratch resistance The scratch resistance test was performed under the following conditions using a scratch automatic tester (manufactured by Profid Co., Ltd.) to evaluate the scratch resistance.
Pressing load: 15 N
Speed: 100 mm / s
The evaluation criteria for scratch resistance are as follows.
○: no blanching wounds found
X: A whitening wound is recognized.

<Manufacture of olefin resin (β)>
Hereinafter, production examples of the olefin resin (β) will be described. In addition, in order to secure the sample amount required for evaluation, the manufacturing process may be implemented in multiple times.

Production Example 1 Production of Olefin-Based Resin (β-1) A stainless steel polymerizer with an internal volume of 100 L equipped with a stirring blade (the number of revolutions of stirring: 250 rpm, internal temperature: 110 ° C., polymerization pressure: 1.0 MPa · G) The following compound (1) is 0.0097 mmol / hour, the following compound (2) is 0.0015 mmol / hour, triphenylcarbenium tetrakis (pentafluorophenyl) borate as a catalyst. Continuously supply triisobutylaluminum at a rate of 2.03 mmol / hr with 0.043 mmol / hr, the gas composition in the gas phase polymerizer is 0.33 (molar ratio) as 1-butene / ethylene, hydrogen / By continuously supplying 1-butene, ethylene and hydrogen so as to obtain 0.42 (molar ratio) as ethylene, a polymerization solution to be produced is obtained. Via the discharge port provided in the engager side wall was continuously discharged while adjusting the degree of opening of the liquid level control valve so as to maintain the polymerization vessel inner solution volume 28L. The resulting polymerization solution is introduced into a heater and heated to 180 ° C., methanol as a catalyst deactivator is added at 80 mL / hour to stop the polymerization, and continuously transferred to the depressurization step under reduced pressure. By drying, an olefin resin (β-1) was obtained at a production rate of 5.8 kg / hour. The analysis results of the obtained olefin resin (β-1) are shown in Table 1.

Production Example 2 Production of Olefin-Based Resin (β′-1) A stainless steel polymerizer with an internal volume of 100 L equipped with a stirring blade (the number of revolutions of stirring: 250 rpm, internal temperature: 110 ° C., polymerization pressure: 1.0 MPa · G) And 23 L / hour of dehydrated hexane, 0.0053 mmol / hour of the compound (1) as a catalyst, 0.021 mmol / hour of triphenylcarbenium tetrakis (pentafluorophenyl) borate as a catalyst, and triisobutylaluminum 2. It is continuously fed at a rate of 2 mmol / hour, and the gas composition in the gas phase polymerizer is 0.23 (molar ratio) as 1-butene / ethylene and 0.017 (molar ratio) as hydrogen / ethylene. The polymerizer is continuously supplied with 1-butene, ethylene and hydrogen, and the resulting polymerization solution is discharged through the outlet provided in the side wall of the polymerizer. The fluid was discharged continuously while adjusting the opening of the liquid level control valve so as to maintain the internal solution amount of 28 L. The resulting polymerization solution is introduced into a heater and heated to 180 ° C., methanol as a catalyst deactivator is added at 80 mL / hour to stop the polymerization, and continuously transferred to the depressurization step under reduced pressure. The olefin resin (β′-1) was obtained at a production rate of 2.1 kg / hour by drying. The analysis results of the obtained olefin resin (β′-1) are shown in Table 1.

<Production of propylene-based polymer (α)>

Production Example 3 Production of Propylene-Based Block Copolymer (α-1) (1) Preparation of Solid Titanium Catalyst Component (A) Four grinding pots with an internal volume of 4 L containing 9 kg of steel balls with a diameter of 12 mm The equipped vibration mill was prepared. In a nitrogen atmosphere, 300 g of magnesium chloride, 115 mL of diisobutyl phthalate, and 60 mL of titanium tetrachloride were added to each pot and ground for 40 hours. 75 g of the obtained co-ground material was placed in a 5 L flask, 1.5 L of toluene was added, and the mixture was stirred at 114 ° C. for 30 minutes and then allowed to stand to remove the supernatant. Next, the solid was washed three times with 1.5 L of n-heptane at 20 ° C., and further dispersed in 1.5 L of n-heptane to obtain a transition metal catalyst component slurry. The obtained solid titanium catalyst component (A) contained 2% by mass of titanium and contained 18% by mass of diisobutyl phthalate.

(2) Preparation of Prepolymerization Catalyst A stirrer with an internal volume of 200 L, 115 g of solid titanium catalyst component (A), 65.6 mL of triethylaluminum, 22.1 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 115 L of heptane. The autoclave was charged with 1150 g of propylene while maintaining the internal temperature at 5 ° C., and reacted while stirring for 60 minutes. After completion of the polymerization, 15.8 mL of titanium tetrachloride was charged to obtain a prepolymerization catalyst (catalyst slurry).

(3) Main polymerization In a vessel polymerizer with a stirrer having an internal volume of 1000 L, 159 kg / hour of propylene, 1.4 g / hour of the catalyst slurry prepared in (2) above as a solid catalyst component, 21.9 mL of triethylaluminum, 2.8 mL / hour of dicyclopentyldimethoxysilane was continuously supplied, and hydrogen was supplied such that the hydrogen concentration in the gas phase became 13.4 mol%. The polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.6 MPa / G.
The obtained slurry was sent to a 500 L internal vessel equipped with a stirrer and subjected to further polymerization. The polymerizer was fed with 37 kg / hour of propylene and hydrogen so that the hydrogen concentration in the gas phase became 11.5 mol%. The polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.4 MPa / G.
The obtained slurry was sent to a 500 L internal vessel equipped with a stirrer and subjected to further polymerization. The polymerizer was supplied with 19 kg / hour of propylene and hydrogen so that the hydrogen concentration in the gas phase became 8.0 mol%. The polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.4 MPa / G.
The obtained slurry was sent to a 500 L internal vessel equipped with a stirrer and subjected to further polymerization. The polymerizer was charged with 15 kg / hour of propylene, hydrogen such that the hydrogen concentration in the gas phase was 0.27 mol%, the polymerization temperature was 65 ° C., and the pressure was 3.2 MPa / G. Diethylene glycol ethyl acetate was added at a 26-fold molar ratio per titanium component in the solid titanium catalyst component (A).
After deactivating and evaporating the obtained slurry, gas-solid separation was performed. The resulting propylene block copolymer (α-1) was vacuum dried at 80 ° C. Physical properties of propylene block copolymer (α-1) are shown in Table 2.

Example 1
20 parts by mass of the olefin resin (β-1) prepared in Production Example 1, 60 parts by mass of the propylene block copolymer (α-1) prepared in Production Example 3, talc as an inorganic filler (trade name: JM 209, After 20 parts by mass of Asada Powder Co., Ltd. product were mixed with a tumbler, they were melt-kneaded under the following conditions with a twin-screw extruder to prepare a pellet-like propylene resin composition 1. Test pieces were produced using the pellet-like propylene-based resin composition 1 under the following conditions with an injection molding machine. Physical properties of the obtained propylene resin composition 1 are shown in Table 3. In addition, the result of the damage resistance test of the propylene-type resin composition 3 is shown in FIG.1 (b).

<Melting and kneading conditions>
Coaxial twin screw kneader: NR-2-36 (trade name, manufactured by Nakatani Machine Co., Ltd.)
Kneading temperature: 190 ° C
Screw speed: 200 rpm
Feeder speed: 500 rpm

<ISO test piece / injection molding condition>
Injection molding machine: NEX110 (made by Nissei Resin Industry Co., Ltd.)
Cylinder temperature: 195 ° C
Mold temperature: 40 ° C
Injection time-Holding time: 42 seconds Cooling time: 10 seconds Screw speed: 100 rpm
Holding pressure: 50MPa
Back pressure: 5MPa

<Square plate (mirror surface) / injection molding conditions>
Injection molding machine: J100 EII-P (manufactured by Japan Steel Works, Ltd.)
Cylinder temperature: 220 ° C
Mold temperature: 40 ° C
Injection time-Hold time: 18 seconds Cooling time 5 seconds Screw speed: 65 rpm
Holding pressure: 8MPa (first stage), 25 to 29MPa (second stage)
Back pressure: 5MPa

Example 2
A pellet-like propylene-based resin composition 2 is prepared in the same manner as in Example 1 except that 55 parts by mass of a propylene-based homopolymer (α-1) and 25 parts by mass of talc are used in Example 1, and injection molding is performed. The test piece was produced by the machine. Physical properties of the obtained propylene-based resin composition 2 are shown in Table 3. In addition, the result of the damage resistance test of the propylene-type resin composition 2 is shown in FIG.2 (b).

Comparative Example 1
A pellet-like propylene-based resin is prepared in the same manner as in Example 1 except that the olefin-based resin (β'-1) prepared in Production Example 2 is used in place of the olefin-based resin (β-1) in Example 1. Composition C1 was prepared, and a test piece was produced by an injection molding machine. Physical properties of the obtained propylene resin composition C1 are shown in Table 3. In addition, the result of the damage resistance test of propylene-type resin composition C1 is shown to Fig.1 (a).

Comparative Example 2
A pellet-like propylene-based resin is prepared in the same manner as in Example 2 except that the olefin-based resin (β'-1) prepared in Production Example 2 is used in place of the olefin-based resin (β-1) in Example 2. Composition C2 was prepared, and a test piece was produced by an injection molding machine. Physical properties of the obtained propylene resin composition C2 are shown in Table 3. In addition, the result of the damage resistance test of the propylene-type resin composition C2 is shown to Fig.2 (a).

  Low temperature of molded article according to Comparative Example 1 obtained from a propylene-based resin composition containing an olefin-based resin (β'-1) not satisfying the requirements defined in the present invention and a propylene-based homopolymer (α-1) The balance of impact strength (HRIT) and hardness and scratch resistance are replaced with the olefin resin (β'-1), and the olefin resin (β-1) satisfying all the requirements (I), (IV) and (V) It can be seen that the improvement is achieved by using (Example 1). Also, it can be seen that the heat distortion temperature (HDT) is also improved. The same tendency applies to the comparison between Comparative Example 2 and Example 2 in which the content of the propylene homopolymer (α-1) is 55 parts by mass and the content of talc is 25 parts by mass. Is recognized.

Claims (8)

70 parts by weight or more and less than 80 parts by weight of a propylene-based polymer (α) having a melt flow rate (MFR) at 0.10 to 500 g / 10 min at 230 ° C. and a load of 2.16 kg obtained according to ASTM D1238E And 20 parts by mass or more but 30 parts by mass or less of the olefin-based resin (β) satisfying the following requirements (I), (IV) and (V) other than the propylene-based polymer (α) The total of 100 parts by mass of α) and the olefin resin (β) is 100 parts by mass, and the inorganic filler is contained in an amount of 0 to 30 parts by mass with respect to a total of 100 parts by mass of α and β And a propylene-based resin composition having a flexural modulus measured according to JIS K7171 in the range of 600 to 2500 MPa.
(I) The olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene / α-olefin copolymer and a side chain made of an ethylene polymer.
(IV) Glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of -80 to -30 ° C.
(V) The intrinsic viscosity [粘度] measured in decalin at 135 ° C. is in the range of 0.1 to 12 dl / g. The propylene-based resin composition according to claim 1, wherein the olefin-based resin (β) further satisfies the following requirements (II) and (III).
(II) A melting peak is shown in the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC), and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The proportion E of the ortho-dichlorobenzene soluble component at 20 ° C. or less measured by cross fractionation chromatography (CFC) is 60 mass% or less.   The propylene-based resin composition according to claim 1 or 2, wherein the weight-average molecular weight of the ethylene polymer constituting the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 10,000.   The propylene according to any one of claims 1 to 3, wherein side chains are present at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain of the graft type olefin polymer [R1]. Resin composition. The propylene resin composition according to any one of claims 1 to 4, wherein the olefin resin (β) further satisfies the following requirement (VI).
(VI) MFR of olefin resin (β) at 190 ° C. and a load of 2.16 kg obtained according to ASTM D 1238 E is M (g / 10 min), and olefin system measured in decalin at 135 ° C. When the intrinsic viscosity [η] of the resin (β) is H (g / dl), the value A represented by the following formula (Eq-1) is in the range of 30 to 280.
A = M / exp (−3.3H) (Eq-1) It is a manufacturing method of the propylene system resin composition as described in any one of Claims 1-5,
At least the olefin resin (β) is selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing the following components (A) to (C): A method for producing a propylene-based resin composition, which is produced by a method comprising the step of copolymerizing one α-olefin.
(A) Bridged metallocene compound represented by the following formula (I) (B) Transition metal compound represented by the following formula [B] (C) (C-1) Organometallic compound, (C-2) organoaluminum oxy At least one compound selected from the group consisting of a compound, and (C-3) a compound which reacts with the bridged metallocene compound (A) or the transition metal compound (B) to form an ion pair
(In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group Two adjacent groups 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 the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-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 the group consisting of heteroatom-containing groups other than silicon-containing group and a silicon-containing group, an R ⁶ and R ⁷ are bonded to each other to form a ring R ¹⁰ and R ¹¹ may be combined with each other to form a ring, provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair And j each 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 as or different from each other. )
(In the formula [B],
M represents a transition metal atom of Group 4 or 5 of the periodic table.
m is an integer of 1 to 4;
R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms represented by the general formula C _{n ′} H _{2 n ′ + 1} (n ′ is an integer of 1 to 8).
R ^{2 to} R ⁵ each independently represent 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, a phosphorus containing group, a silicon containing A group, a germanium-containing group, or a tin-containing group is shown, and two or more of these may be bonded to each other to form a ring.
R ^{6 to} R ^{8 each} represent a hydrocarbon group, at least one of which is an aromatic hydrocarbon group, and when m is an integer of 2 or more, R may be R between structural units of the formula [B] ^Two groups among the groups represented by ^{2 to} R ⁸ may be linked.
n is a number satisfying the valence of M, 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, And X represents 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, plural Xs may be the same or different. In addition, a plurality of groups represented by X may be bonded to each other to form a ring. )   The method for producing a propylene-based resin composition according to claim 6, wherein the step of copolymerization is a step of copolymerization by a solution polymerization method in a temperature range of 80 to 300 ° C.   The molded object using the propylene-type resin composition as described in any one of Claims 1-5.