JP2017057314A - Propylene-based resin composition, production method thereof, and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based resin composition excellent in balance between the rigidity and the shock resistance.SOLUTION: A propylene-based resin composition contains 50-98 pts.mass of a propylene-based resin (α), and 2-50 pts.mass of an olefin-based resin (β) other than the propylene-based resin (α) satisfying prescribed requirements, where the propylene-based resin (α) and the olefin-based resin (β) sum up to 100 pts.mass.SELECTED DRAWING: None

Description

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

  Among olefin resins, propylene resin is used in various fields such as daily goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, etc. A propylene-based resin composition containing these additives is used. In addition, as an effort to 3R (Reduce, Reuse, Recycle) to form a recycling society, attempts have been made to reduce the weight of thin molded products in each industrial field recently. Improvement of the propylene-based resin composition is being promoted so that sufficient rigidity and impact resistance can be obtained even if the molded product is reduced in weight and thickness.

  Polypropylene block copolymers are industrially produced as polypropylene with improved impact resistance and are widely used in the aforementioned applications. This block copolymer is also called an impact copolymer or a heterophasic copolymer. That is, in a multi-stage polymerization process, following the homopolymer polymerization, ethylene is copolymerized in a subsequent reaction vessel to produce a composition containing an ethylene-propylene polymer. The block copolymer produced in this way has a structure (sea-island structure) in which the “island” of the ethylene-propylene polymer floats in the “sea” of the homopolymer. Excellent impact strength. The term “block” in this polypropylene block copolymer does not mean “block copolymer”. That is, the polypropylene block copolymer is not a homopolypropylene chain and an ethylene-propylene copolymer chain chemically bonded, and can be said to be a two-stage polymerization composition.

  For example, in Patent Document 1, a metallocene-catalyzed propylene block copolymer composition, an elastomer and an inorganic filler, in which two components of an ethylene-propylene copolymer rubber part having a low ethylene content and a high content are present. A propylene-based resin composition comprising a material is disclosed. Patent Document 2 discloses a propylene block copolymer resin composition containing a high molecular weight propylene / ethylene copolymer rubber. In the propylene-based resin composition described in Patent Document 1 or Patent Document 2, although improvement in impact resistance is recognized, the improvement effect is insufficient for further demand for higher rigidity.

  On the other hand, Patent Document 3 discloses a technique for performing multistage polymerization with a catalyst containing a crosslinked bisindenylzirconocene that generates a vinyl group at the terminal. In the technology of Patent Document 3, propylene is polymerized in the former stage, and some comonomer and polypropylene are copolymerized in the latter stage, so that a part of the polypropylene having a vinyl structure at the terminal produced in the former stage is converted into the main chain in the latter stage polymerization. It is captured. As a result, a composition containing a branched propylene copolymer grafted with polypropylene is obtained. Further, Patent Document 4 and Patent Document 5 disclose a technique for obtaining a branched polymer having a higher molecular weight of the side chain polypropylene by using a crosslinked bisindenyl hafnocene complex-supported catalyst system. The techniques of Patent Documents 3 to 5 have a branched polymer in part, unlike the block copolymer. Due to the presence of this branched polymer, the compatibility between the polypropylene part and the rubber part is increased, and a polypropylene composition having characteristics of excellent transparency and high meltability can be obtained. However, the techniques of Patent Documents 3 to 5 cannot sufficiently increase the melting point of the polypropylene part compared to the polypropylene block copolymer obtained with a general-purpose Ziegler-Natta catalyst system, and limit the comonomer composition and molecular weight of the rubber part. For this reason, it has not been possible to provide a polypropylene resin composition having both sufficient rigidity and impact resistance.

  Against this background, technical development of block polymers (including linear and branched types) in which an ethylene copolymer and polypropylene are combined, which is excellent in polypropylene resin modification performance, is in progress.

  In Patent Document 6 and Patent Document 7, reactive functional groups such as maleic acid, halogen, and leaving metal are introduced into polyolefin, and the ethylene / α-olefin copolymer chain and the crystalline propylene polymer chain are cupped. A method for obtaining a high content of the target polymer composition by ring reaction is disclosed. However, in this method, the reaction process such as the introduction of a functional group into the polymer and the coupling process is complicated and inferior in productivity, and coloring by the by-product and residual substrate generated in each reaction process, an unpleasant odor, contamination by the eluted component, etc. May occur.

  Patent Document 8 discloses a method for obtaining a linear block copolymer comprising an ethylene / α-olefin copolymer chain and a crystalline polypropylene chain by using a reversible chain transfer technique. However, since this method requires a reversible chain transfer agent, it is not economical and has limited applications. On the other hand, a method for economically obtaining a branched copolymer of an ethylene copolymer and polypropylene by using a polymerization catalyst technique is also disclosed. For example, Patent Document 9 and Patent Document 10 show that a branched olefin polymer composition having a main chain soft segment of an ethylene copolymer and a side chain hard segment of polypropylene is useful as a modifier for a polypropylene resin. Is described. Patent Document 9 discloses a composition containing a graft type olefin polymer having an ethylene polymer as a side chain. Patent Document 10 uses a specific polymerization catalyst and is excellent as a thermoplastic elastomer such as an elastic recovery rate. A composition containing a graft olefin polymer having a crystalline propylene polymer as a side chain, which is characterized by exhibiting physical properties, is disclosed.

  However, although the compositions disclosed in Patent Document 9 and Patent Document 10 include a branched olefin polymer having a crystalline propylene polymer as a side chain, the disclosed technology has an efficiency in producing a graft olefin polymer. When the composition is low and blended with polypropylene resin, the balance of physical properties is insufficiently improved. In order to obtain a branched copolymer excellent in reforming performance introduced with a high content of polypropylene side chains, a terminal vinyl type polypropylene macromonomer produced in the former polymerization can be dissolved well in the latter polymerization. There is a need for a good copolymerizable catalyst that can be efficiently copolymerized and have a high molecular weight at a high temperature (90 ° C. or higher).

JP 2007-2111189 A JP 2003-327758 A JP 2001-525460 A JP 2008-144152 A JP 2009-114404 A JP 2009-102598 A JP 2009-227898 A JP 2013-529705 A JP 2001-527589 A International Publication No. 2013/061974

  An object of this invention is to provide the propylene-type resin composition excellent in the balance of rigidity and impact resistance.

  The present invention relates to the following [1] to [8].

[1] 50 to 98 parts by mass of propylene resin (α) and 2 to 50 parts by mass of olefin resin (β) satisfying the following requirements (I) to (VI) other than the propylene resin (α) A propylene-based resin composition comprising a resin (α) and the olefin-based resin (β) in a total of 100 parts by mass).
(I) The olefin resin (β) includes a graft olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer.
(II) When the ratio of the propylene polymer contained in the olefin resin (β) is P mass%, P is in the range of more than 20 and 60 or less.
(III) The proportion of the component having a differential elution curve peak value of less than 65 ° C. measured by a cross-fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent to the olefin resin (β) is expressed as E mass%. The value a represented by the following formula (Eq-1) is 1.4 or more.

a = (100-E) / P (Eq-1)
(IV) Melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C, and glass transition temperature (Tg) is in the range of -80.0 to -30.0 ° C. is there.
(V) The thermal xylene insoluble amount is 3% by mass or less.
(VI) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 1.8 dl / g.

  [2] The ratio of the units derived from ethylene contained in the olefin resin (β) is in the range of 20 to 80 mol% with respect to the units derived from all monomers contained in the olefin resin (β). Description Propylene-based resin composition.

  [3] The isopropyl pentad fraction (mmmm) of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is 93% or more, [1] or [2] Propylene-based resin composition.

  [4] The weight average molecular weight of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is in the range of 5,000 to 100,000, according to any one of [1] to [3]. Propylene-based resin composition.

  [5] The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft type olefin polymer [R1] is in the range of 50,000 to 200,000. The propylene-type resin composition in any one.

[6] A method for producing a propylene-based resin composition according to any one of [1] to [5],
The manufacturing method of the propylene-type resin composition which manufactures the said olefin resin ((beta)) with the method of including the following process (A) and process (B).

(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process,
(B) In the presence of a catalyst for olefin polymerization containing a crosslinked metallocene compound represented by the following formula [B], the terminal unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms. A step of copolymerizing at least one α-olefin selected from the group consisting of:

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. And a group adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group.

R ⁷ and R ¹⁰ 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 heteroatom-containing group other than a silicon-containing group.

R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represents an aryl group.

Y ¹ represents a carbon atom or a silicon atom.

M ¹ represents a zirconium atom or a hafnium atom.

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

  [7] The method for producing a propylene-based resin composition according to [6], wherein the step (B) is a solution polymerization step in which copolymerization is performed at 90 ° C. or higher.

  [8] A molded product of the propylene-based resin composition according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the propylene-type resin composition excellent in the balance of rigidity and impact resistance can be provided.

It is the graph which showed the relationship between the ratio E (mass%), the ratio P (mass%), and a value.

  The propylene resin composition according to the present invention comprises 50 to 98 parts by mass of a propylene resin (α) and an olefin resin (β) 2 that satisfies the requirements (I) to (VI) other than the propylene resin (α). ~ 50 parts by mass. In addition, the sum total of the said propylene-type resin ((alpha)) and the said olefin resin ((beta)) is 100 mass parts.

  55-95 mass parts is preferable, as for content of propylene-type resin ((alpha)), 60-90 mass parts is more preferable, 65-85 mass parts is further more preferable, and 65-80 mass parts is especially preferable. Moreover, 5-45 mass parts is preferable, as for content of olefin resin ((beta)), 10-40 mass parts is more preferable, 15-35 mass parts is further more preferable, and 20-35 mass parts is especially preferable. Impurity and toughness are improved while maintaining the original properties of propylene resin, such as rigidity and hardness, because the content ratio of propylene resin (α) and olefin resin (β) is within the above range. Therefore, the propylene-based resin composition can be suitably used for production of various molded products.

<Propylene resin (α)>
As the propylene-based resin (α), for example, a propylene homopolymer, a copolymer of propylene and at least one selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms can be used. . The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2- Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene Dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, Decene, 1-undecene, 1-dodecene, and the like. Among these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  The propylene resin (α) may be composed of a single propylene resin or may be composed of a plurality of propylene resins. The propylene resin (α) can be obtained by polymerization using, for example, a Ziegler-Natta catalyst.

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

  Homopolypropylene resin is a resin composed essentially of a propylene homopolymer, is inexpensive and easy to produce, and is inferior in impact resistance and toughness on the other hand, having excellent rigidity and surface hardness. In the propylene-based resin composition according to the present invention, when a homopolypropylene resin is used as the propylene-based resin (α), the olefin-based resin (β) retains the characteristics such as the rigidity of the homopolypropylene resin, while maintaining the impact resistance. And the toughness can be improved.

  The random polypropylene resin is a resin mainly composed of a propylene polymer containing a small amount of a comonomer, and has higher impact resistance and transparency than a homopolypropylene resin. In the propylene resin composition according to the present invention, when a random polypropylene resin is used as the propylene resin (α), the olefin resin (β) retains the rigidity of the random polypropylene resin, while maintaining impact resistance, toughness, and The surface hardness can be improved, and particularly the low temperature impact property can be improved.

  The block polypropylene resin is a two-stage polymerization composition of a propylene polymer and an ethylene propylene copolymer, and the term “block” in the block polypropylene resin does not mean “block copolymer”. Since the block polypropylene resin contains an ethylene propylene copolymer, the balance between rigidity and impact resistance is improved as compared with the homopolypropylene resin. In the propylene-based resin composition according to the present invention, when a block polypropylene resin is used as the propylene-based resin (α), the olefin-based resin (β), such as rigidity and impact resistance, cannot be achieved by the block polypropylene resin alone. The reciprocal physical properties can be improved in a highly balanced manner.

  The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the propylene-based resin (α) is preferably 0.1 to 500 g / 10 minutes, more preferably 0.2 to 300 g / 10 minutes, 0 3 to 100 g / 10 min is more preferable, and 0.4 to 50 g / 10 min is particularly preferable. When the MFR of the propylene resin (α) is 0.1 g / 10 min or more, the dispersibility of the propylene resin (α) and the olefin resin (β) in the propylene resin composition is improved, and the resin The mechanical strength of the composition is improved. Moreover, when MFR of propylene-type resin ((alpha)) is 500 g / 10min or less, the intensity | strength of propylene-type resin ((alpha)) itself improves and the mechanical strength of a resin composition improves. In addition, MFR becomes a parameter | index of the molecular weight of propylene-type resin ((alpha)).

  The polypropylene-converted weight average molecular weight of the propylene-based resin (α) determined by gel permeation chromatography (GPC) is preferably 80,000 to 900,000, more preferably 100,000 to 700,000, and 150,000 to 700,000. Further preferred.

  The tensile elastic modulus of the propylene-based resin (α) is preferably 500 to 3000 MPa, more preferably 600 to 2500 MPa, and further preferably 650 to 2200 MPa. When the tensile elastic modulus is within the above range, the propylene-based resin composition exhibits high rigidity and high hardness. The tensile modulus is a value measured at 23 ° C. using a 2 mm thick press sheet in accordance with JIS K7113-2.

  The propylene resin (α) is different from the propylene polymer contained in the olefin resin (β). Substantially the terminal structure of the propylene-based resin (α) can be a saturated hydrocarbon, specifically, the proportion of terminal unsaturation can be less than 0.1 per 1000 carbon atoms.

<Olefin resin [β]>
The olefin resin (β) according to the present invention is an olefin resin other than the propylene resin (α) and satisfies all of the following requirements (I) to (VI). The olefin resin (β) preferably satisfies at least one of the following requirements (VII) to (IX). In addition, olefin resin ((beta)) may be comprised by 1 type, and may be comprised from 2 or more types of olefin resin.
(I) The olefin resin (β) includes a graft olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer.
(II) When the ratio of the propylene polymer contained in the olefin resin (β) is P mass%, P is in the range of more than 20 and 60 or less.
(III) The ratio with respect to the olefin resin (β) of the component having a differential elution curve peak value of less than 65 ° C. measured by a cross-fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent is defined as E mass%. When the value a represented by the following formula (Eq-1) is 1.4 or more.

a = (100-E) / P (Eq-1)
(IV) Melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C, and glass transition temperature (Tg) is in the range of -80.0 to -30.0 ° C. is there.
(V) The thermal xylene insoluble amount is 3% by mass or less.
(VI) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 1.8 dl / g.
(VII) The ratio of the ethylene-derived unit contained in the olefin resin (β) is 20 to 80 mol% with respect to the units derived from all monomers contained in the olefin resin (β).
(VIII) The heat of fusion ΔH at the melting peak measured by differential scanning calorimetry (DSC) is in the range of 5 to 50 J / g.
(IX) The proportion of the orthodichlorobenzene-soluble component at 50 ° C. or lower measured by a cross fractionation chromatograph (CFC) is 50% by mass or lower.

  Details of each requirement will be described below.

(Requirement (I))
The olefin resin (β) includes a graft olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer. The graft type olefin polymer [R1] is a graft copolymer having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer. In the present invention, the “graft copolymer” refers to a polymer in which one or more side chains are bonded to the main chain.

  The graft type olefin polymer [R1] has a structure in which a side chain made of a propylene polymer is chemically bonded to a main chain made of an amorphous or low crystalline ethylene / α-olefin copolymer. The olefin resin (β) containing the graft type olefin polymer [R1] exhibits higher compatibility than the propylene resin containing a linear ethylene / α-olefin copolymer. For this reason, the propylene-type resin composition containing an olefin resin ((beta)) and the said propylene-type resin ((alpha)) can express the outstanding physical property balance.

The main chain and side chain of the graft type olefin polymer [R1] preferably satisfy the following requirements (i) to (iv).
(I) The main chain consists of units derived from ethylene and units derived from at least one α-olefin selected from the group consisting of C 3-20 α-olefins, and these α-olefin derived units. Is in the range of 10 to 50 mol% with respect to the units derived from all monomers contained in the main chain.
(Ii) The ethylene / α-olefin copolymer constituting the main chain has a weight average molecular weight of 50,000 to 200,000.
(Iii) The side chain consists essentially of units derived from propylene.
(Iv) The weight average molecular weight of the propylene polymer constituting the side chain is 5,000 to 100,000.

  Details of each requirement will be described below.

(Requirement (i))
The main chain of the graft-type olefin polymer [R1] consists of ethylene-derived units and at least one α-olefin-derived unit selected from the group consisting of α-olefins having 3 to 20 carbon atoms, It is preferable that the ratio of the unit derived from the α-olefin is in the range of 21 to 50 mol% with respect to the units derived from all monomers contained in the main chain.

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

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1- Butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1 -Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, Nonene, 1-decene, 1-undecene, 1-dodecene, and the like.

  The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Branched olefins such as 3-methyl-1-butene are preferred, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are more preferred, 1-butene, 1-pentene, 1-hexene and 1-hexene. Octene is more preferred. In particular, by using 1-butene, 1-pentene, 1-hexene, or 1-octene as the α-olefin having 3 to 20 carbon atoms, a propylene-based resin having a particularly good balance of physical properties between rigidity and impact resistance. A resin composition is obtained.

  The proportion of ethylene-derived units in the main chain of the graft-type olefin polymer [R1] is preferably 50 to 90 mol% with respect to units derived from all monomers contained in the main chain, and is preferably 60 to 90 mol%. It is more preferable that Moreover, the ratio of the unit derived from the at least 1 sort (s) of alpha olefin selected from the group which consists of a C3-C20 alpha olefin is 10-50 mol% with respect to the unit derived from all the monomers contained in a principal chain. It is preferable that it is 10-40 mol%. Depending on the type of α-olefin to be used, the relationship between the ratio of units derived from ethylene and α-olefin and the glass transition temperature (Tg) is different, but to achieve the range of the glass transition temperature (Tg) of the requirement (IV). The ratio of units derived from ethylene and α-olefin in the main chain of the graft type olefin polymer [R1] is preferably within the above range. Moreover, since the ratio of the unit derived from ethylene and α-olefin in the main chain is within the above range, the olefin resin (β) is flexible and has excellent low-temperature characteristics. The propylene-based resin composition containing β) is excellent in low-temperature impact resistance. On the other hand, when the unit derived from α-olefin is less than 10 mol%, the resulting olefin resin (β) is inferior in flexibility and low temperature characteristics, and the propylene resin composition containing the resin is inferior in low temperature impact resistance. There is a case.

  The molar ratio of ethylene and α-olefin-derived units in the main chain is controlled by controlling the ratio between the concentration of ethylene and the concentration of α-olefin present in the polymerization reaction system in the step of producing the main chain. Can be adjusted. The molar ratio of α-olefin-derived units contained in the main chain is, for example, the α-olefin composition of an ethylene / α-olefin copolymer obtained under the conditions not containing terminal unsaturated polypropylene, which will be described later. Or by subtracting the influence derived from the terminal unsaturated polypropylene or the side chain from the α-olefin composition of the olefin resin (β).

(Requirement (ii))
The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft olefin polymer [R1] is preferably in the range of 50,000 to 200,000. In the propylene-based resin composition according to the present invention, from the viewpoint of improving resin moldability (fluidity) while maintaining mechanical strength, the weight average molecular weight is more preferably in the range of 100,000 to 200,000, and 120,000. More preferably, it is in the range of ˜180,000.

  When the weight average molecular weight is within the above range, the propylene resin composition containing the olefin resin (β) tends to have a better balance between impact resistance, rigidity, and toughness. On the other hand, when the weight average molecular weight is less than 50000, impact resistance and toughness may be lowered. Moreover, when the said weight average molecular weight exceeds 200000, the dispersion | distribution defect to propylene-type resin will occur, and it may become difficult to obtain a desired physical property balance.

  The said weight average molecular weight can be adjusted by controlling the ethylene concentration in a polymerization system in the manufacturing process mentioned later. Examples of the ethylene concentration control method include adjustment of ethylene partial pressure and polymerization temperature. The weight average molecular weight can also be adjusted by supplying hydrogen into the polymerization system.

  In addition, the said weight average molecular weight is a weight average molecular weight of polyethylene conversion calculated | required by gel permeation chromatography (GPC). The weight average molecular weight is determined by, for example, analyzing an ethylene / α-olefin copolymer produced under conditions not containing terminal unsaturated polypropylene, which will be described later, or analyzing an olefinic resin (β). It is obtained from subtracting the effects derived from polypropylene and side chains.

(Requirement (iii))
The side chain of the graft type olefin polymer [R1] is preferably substantially composed of units derived from propylene. In particular, the side chain of the graft-type olefin polymer [R1] is preferably a propylene polymer having isotactic regularity substantially composed of units derived from propylene.

  A propylene polymer consisting essentially of propylene-derived units is a propylene polymer whose molar ratio of propylene-derived units is 99.5 to 100 mol% with respect to units derived from all monomers contained in the propylene polymer. Can show coalescence. That is, a small amount of α-olefin other than propylene may be copolymerized within a range that does not impair its role and characteristics.

  In particular, the isotactic pentad fraction (mmmm) of the propylene polymer constituting the side chain of the graft-type olefin polymer [R1] is preferably 93% or more, and 93.2% or more. Is more preferably 93.5% or more. When the mmmm is within the above range, the side chain exhibits crystallinity and has a melting point. When the side chain is an isotactic poly (propylene) polymer having a high melting point, the compatibility of the olefin resin (β) with the propylene resin is improved. For this reason, the obtained propylene-based resin composition can maintain good rigidity and hardness while expressing good impact resistance.

  Graft type olefin polymer [R1], for example, copolymerizes terminally unsaturated polypropylene produced in step (A) with ethylene and α-olefin in the production step (B) of olefin resin (β) described later. Can be obtained. That is, the composition and stereoregularity of the terminal unsaturated polypropylene correspond to the side chain composition and stereoregularity of the graft-type olefin polymer [R1]. Therefore, the composition and stereoregularity of the terminal unsaturated polypropylene produced in the step (A) are calculated using a known method, and the composition and stereoregularity are calculated based on the side chain composition of the graft-type olefin polymer [R1]. And stereoregularity. Specifically, mmmm is a value measured by a method described later.

(Requirement (iv))
The weight average molecular weight of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is preferably in the range of 5,000 to 100,000. That is, the graft type olefin polymer [R1] has a structure in which a macromonomer, which is a propylene polymer having a weight average molecular weight of 5000 to 100,000, is bonded to an ethylene / α-olefin copolymer. The site is preferably a side chain. The weight average molecular weight is more preferably 5000 to 60000, and further preferably 5000 to 25000.

  When the weight average molecular weight is within the above range, the compatibility between the propylene resin (α) and the olefin resin (β) increases, and the propylene contains the propylene resin (α) and the olefin resin (β). The impact resistance and elongation at break of the resin-based resin composition are well expressed, and the fluidity during injection molding is also good. On the other hand, when the weight average molecular weight is less than 5,000, the interfacial strength with the propylene resin (α) becomes weak, and the elongation and impact resistance of the propylene resin composition may be lowered. Moreover, when the said weight average molecular weight exceeds 100,000, the fluidity | liquidity at the time of shaping | molding of the resin composition containing an olefin resin ((beta)) may become low, and workability may fall. In addition, the compatibility between the propylene resin (α) and the olefin resin (β) decreases, and the tensile elongation and resistance of the propylene resin composition containing the propylene resin (α) and the olefin resin (β) are reduced. In some cases, the impact property is lowered, or the surface hardness of a molded product obtained from the propylene-based resin composition is lowered.

  Examples of the method for adjusting the weight average molecular weight include a method for adjusting the polymerization temperature and the polymerization pressure in the production step (A) described later.

  In addition, the said weight average molecular weight can be calculated | required by measuring the weight average molecular weight of the terminal unsaturated polypropylene produced | generated at a process (A) by a conventional method similarly to the said requirement (iii). For example, the weight average molecular weight in terms of polypropylene of the terminal unsaturated polypropylene determined by gel permeation chromatography (GPC) can be used as the weight average molecular weight of the propylene polymer constituting the side chain.

(Requirement (II))
When the ratio (hereinafter also referred to as ratio P) of the propylene polymer contained in the olefin resin (β) is P mass%, P is in the range of more than 20 and 60 or less. Here, the propylene polymer contained in the olefin resin (β) is, for example, a polypropylene side chain incorporated into the main chain in the step (B) described later, and a polypropylene linear polymer not incorporated into the main chain. Indicates the sum of The ratio P exceeds 20% by mass, preferably 50% by mass or less, more than 20% by mass, more preferably 40% by mass or less, and further preferably 25% by mass or more and 40% by mass or less.

  When the ratio P is within the above range, the compatibility between the propylene resin (α) and the olefin resin (β) increases, and the propylene resin contains the propylene resin (α) and the olefin resin (β). The impact resistance of the composition is well expressed. On the other hand, when the ratio P is 20% by mass or less, the compatibility with the propylene-based resin (α) is low, and the resulting propylene-based resin composition does not exhibit good physical properties in impact resistance. Moreover, when the ratio P exceeds 60 mass%, the content of the relative ethylene / α-olefin copolymer is decreased, and the resulting propylene resin composition does not exhibit good physical properties in terms of low-temperature impact resistance.

  The ratio P is calculated | required from the ratio of the mass of the terminal unsaturated polypropylene used for the process (B) mentioned later, for example, and the mass of the obtained olefin resin ((beta)).

  In addition, terminal unsaturated polypropylene means the polypropylene which has terminal unsaturation represented by the following terminal structure (I)-(IV). “Poly” in the terminal structures (I) to (IV) indicates a bonding position between the terminal structure and a propylene polymer molecular chain other than the terminal structure.

  The ratio of terminal unsaturation in the terminal unsaturated polypropylene is preferably from 0.1 to 10 and more preferably from 0.4 to 5.0 per 1000 carbon atoms. Furthermore, the ratio of terminal unsaturation represented by the terminal structure (I) generally called terminal vinyl is preferably from 0.1 to 2.0 per 1000 carbon atoms, and from 0.4 to 2.0 More preferred.

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

  For example, in the case of the terminal structure (I), assuming that the integral value of δ4.9 to 5.1 (2H) is A and the total integral value derived from the propylene polymer is B, the terminal structure per 1000 carbon atoms (I ) Is obtained as 1000 × (A / 2) / (B / 2). When determining the ratio of other terminal structures, it may be replaced with the integrated value of the peak attributed to each structure in consideration of the ratio of hydrogen.

(Requirement (III))
The olefin resin (β) is a ratio of a component having a differential elution curve peak temperature of less than 65 ° C. measured by a cross fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent to the olefin resin (β) ( Hereinafter, when the ratio E) is E mass%, the value a (hereinafter also referred to as a value) represented by the following formula (Eq-1) is 1.4 or more. In the following formula (Eq-1), P represents the ratio P.

a = (100-E) / P (Eq-1)
The a value is preferably 1.6 or more, and more preferably 2.2 or more.

The differential elution curve is obtained by differentiating the cumulative elution curve obtained in the elution temperature range of -20 ° C to 140 ° C. Furthermore, the component ratio of each elution peak can be obtained by separating each elution peak appearing in the differential elution curve into a normal distribution curve. Here, the ratio of soluble components below −20 ° C. (the proportion of components not coated in the temperature rising elution fractionation (TREF) column even at −20 ° C. in the cooling step of CFC measurement) is E _{(<−20 ° C.)} mass. %, - the sum of the percentage of eluted component having a peak at less than 20 ° C. or higher _{65 ℃ E (<65 ℃)} mass%, the sum of the percentage of eluted component having a peak below 140 ° C. 65 ° C. or more E _{(≧ 65 C))} mass%, and the ratio of components that do not dissolve at 140 ° C. is E _{(> 140 ° C.)} mass%, and E _{(<−20 ° C.)} + E _{(<65 ° C.)} + E _{(≧ 65 ° C.)} + E _{(> 140 ° C.)} = 100 In the case of mass%, the ratio is defined as E = E _{(<−20 ° C.)} + E _{(<65 ° C.)} . In general, the olefin resin (β) is completely soluble in orthodichlorobenzene at 140 ° C., and a clear peak that is easily separated at 65 ° C. or higher can be detected. Therefore, E _{(> 140 ° C.)} = In the case of 0, the ratio E = 100−E _{(≧ 65 ° C.)} is defined.

  As a detector in the CFC measurement, an infrared spectrophotometer (detection wavelength: 3.42 μm) can be used. Specifically, the CFC measurement can be performed by a method described later.

  The ratio E and the ratio P are ratios relative to the total amount of the olefin resin (β), but the total amount indicates, for example, only the resin obtained through the polymerization step described later, and the separately added resins, additives, etc. Is not included.

  That the a value is within the above range corresponds to that the olefin resin (β) is a graft type olefin polymer [R1], that is, an ethylene / α-olefin copolymer having a propylene polymer portion as a side chain. The amount is included.

  The relationship between the ratio E (mass%), the ratio P (mass%), and the a value is shown in FIG. In FIG. 1, the dotted line showing the relationship of a = 1.0 indicates the case where the graft type olefin polymer [R1] is not included, that is, the case of a mixture of an ethylene / α-olefin copolymer and a propylene polymer. . On the other hand, as the value a increases and the content of the graft olefin polymer [R1] increases, the value of the ratio E with respect to the ratio P decreases. A large a value indicates that the content of the graft olefin polymer [R1] is high. The olefin resin (β) according to the present invention has a value of 1.4 or more.

  Usually, commercially available olefin elastomers used for polypropylene resin modifiers and the like are composed of ethylene / α-olefin copolymers (for example, ethylene / butene copolymers and ethylene / octene copolymers), and the composition of ethylene. Is a polymer adjusted to about 90 mol% to 50 mol%. Therefore, the ratio E of the elution component of a normal ethylene / α-olefin copolymer is substantially 100%.

  When an olefin-based elastomer composed of an ethylene / α-olefin copolymer is blended in a propylene-based resin, the olefin-based elastomer is dispersed in the propylene-based resin and plays a role of imparting an improvement in impact resistance. Increasing the blending amount of the olefin-based elastomer improves impact resistance, but decreases the original rigidity and mechanical strength of the propylene-based resin. For this reason, generally, in a polypropylene resin composition, impact strength and rigidity are reciprocal properties.

  The olefin resin (β) according to the present invention contains a large amount of graft type olefin polymer [R1] in which a crystalline propylene polymer is chemically bonded to an ethylene / α-olefin copolymer. -The characteristic is that the ratio E is small with respect to the content of the α-olefin copolymer.

  When such an olefin resin (β) is blended with the propylene resin (α), the polypropylene side chain of the graft type olefin polymer [R1] has a good affinity with the propylene resin (α). In particular, it has a feature of forming a phase separation structure in which an ethylene / α-olefin copolymer is finely dispersed in a propylene resin (α). At this time, the polypropylene side chain of the graft-type olefin polymer [R1] is a propylene resin at the interface between the ethylene / α-olefin copolymer and the propylene resin (α) which are incompatible with each other. It is considered that it enters the crystal of (α) and exhibits the effect of increasing the strength of the interface. For this reason, a propylene composition blended with an olefin resin (β) containing a large amount of the graft type olefin polymer [R1] has excellent impact resistance, high rigidity and mechanical strength, and excellent elongation. The surface hardness of the resulting molded article is increased, and the composition has an improved balance of physical properties.

(Requirement (IV))
The olefin resin (β) has a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 120 to 165 ° C., and a glass transition temperature (Tg) of −80.0 to −30.0. Within the range of ° C.

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

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

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

  The glass transition temperature (Tg) is preferably -80.0 to -40.0 ° C, more preferably -80.0 to -50.0 ° C, and further preferably -80.0 to -60.0 ° C. The glass transition temperature (Tg) is mainly attributed to the nature of the ethylene / α-olefin copolymer of the main chain of the graft olefin polymer [R1]. When the glass transition temperature (Tg) is in the range of −80.0 ° C. to −30.0 ° C., the propylene resin composition containing the olefin resin (β) exhibits excellent impact resistance. .

  The glass transition temperature (Tg) can be adjusted by controlling the type and composition of the α-olefin of the ethylene / α-olefin copolymer.

  The measurement of the melting point (Tm) and the glass transition temperature (Tg) by differential scanning calorimetry (DSC) can be specifically carried out by the method described later.

(Requirement (V))
The olefin resin (β) has an insoluble amount of thermal xylene of 3% by mass or less, preferably 2.5% by mass or less, more preferably 2% by mass or less, and 1.5% by mass or less. More preferably. The insoluble amount of hot xylene may be 0% by mass. Since the olefin resin (β) has an insoluble amount of thermal xylene of 3% by mass or less, the olefin resin (β) can be favorably dispersed in the propylene resin (α), and as a result, a desired effect is exhibited. On the other hand, when the amount of the hot xylene insoluble part exceeds 3% by mass, an appearance defect called “butsu” occurs in the molded body obtained from the propylene-based resin composition.

  The thermal xylene insoluble amount is a value calculated by the following method. The sample is formed into a sheet having a thickness of 0.4 mm by hot pressing (180 ° C., heating for 5 minutes, cooling for 1 minute) and cut into pieces. About 100 mg is weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a sealed container. Next, the screen is taken out and dried at 80 ° C. for 2 hours or more until a constant weight is obtained. The thermal xylene insoluble amount (% by mass) is represented by the following formula.

Thermal xylene insoluble amount (% by mass) = 100 × (W3-W2) / (W1-W2)
W1: total mass of screen and sample before test, W2: mass of screen, W3: total mass of screen and sample after test.

  The insoluble amount of hot xylene can be adjusted within the above range by adopting a method of obtaining a graft type olefin polymer directly from the polymerization step, as shown in the production method described later.

(Requirement (VI))
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 1.0 to 1.8 dl / g. The intrinsic viscosity [η] is preferably 1.2 to 1.8 dl / g, more preferably 1.3 to 1.8 dl / g, and still more preferably 1.4 to 1.8 dl / g. When the intrinsic viscosity [η] is within the above range, the propylene resin composition containing the olefin resin (β) has good rigidity and mechanical strength in addition to impact resistance, and further has MFR. Since it can be increased, it also has good moldability. The intrinsic viscosity [η] is a value measured by the method described later.

(Requirement (VII))
The proportion of units derived from ethylene contained in the olefin resin (β) is preferably 20 to 80 mol%, more preferably 30 to 80 mol based on the units derived from all monomers contained in the olefin resin (β). %, More preferably 40 to 80 mol%, particularly preferably 40 to 75 mol%. When the ratio is within the above range, the olefin resin (β) is in an embodiment containing more ethylene / α-olefin copolymer, and the propylene resin composition containing the olefin resin (β) is impact resistant. Good.

(Requirements (VIII))
The olefin resin (β) preferably has a heat of fusion ΔH at a melting peak measured by differential scanning calorimetry (DSC) within a range of 5 to 50 J / g, and within a range of 5 to 40 J / g. More preferably, it is more preferably within the range of 10 to 30 J / g.

  The melting peak is derived from the side chain composed of the propylene polymer of the graft type olefin polymer [R1] and the propylene polymer having terminal unsaturation contained in the olefin resin (β). The amount of heat (ΔH) within the above range indicates that a substantial amount of the side chain site of the graft olefin polymer [R1] contained in the olefin resin (β) is included. In the olefin resin (β) according to the present invention, the presence of the polypropylene side chain of the graft-type olefin polymer [R1] is less sticky and can exhibit physical properties like a heat-resistant elastomer.

  On the other hand, when the amount of heat of fusion (ΔH) is less than 5 J / g, since the proportion of polypropylene side chains is small, it may not have heat resistance and may be highly sticky like a linear olefin-based elastomer. Moreover, the modification effect in the propylene-based resin as described above may not be sufficient. When the heat of fusion (ΔH) exceeds 50 J / g, characteristics derived from the ethylene / α-olefin copolymer such as flexibility and low temperature characteristics may be impaired.

  The heat of fusion ΔH is a value measured by the method described later.

(Requirements (IX))
In the olefin resin (β), the proportion of an orthodichlorobenzene-soluble component at 50 ° C. or less as measured by a cross fractionation chromatograph (CFC) is preferably 50% by mass or less, and 40% by mass or less. Is more preferable.

  By satisfying this requirement (IX) in addition to the requirement (III), the effect of including the graft type olefin polymer [R1] becomes higher, the stickiness of the olefin resin (β) becomes lower, and handling Good. Furthermore, even in the propylene-based composition blended with the olefin resin (β), it has excellent impact resistance, high rigidity and mechanical strength, excellent elongation, and high surface hardness of the resulting molded body, and balance of physical properties. Is presumed to be a further improved composition.

  In addition, the ratio (mass%) of the ortho dichlorobenzene soluble component below 50 degreeC is the accumulation elution amount in 50 degreeC (a -20 degreeC soluble component is included) of the accumulation elution curve by CFC measurement mentioned later.

  It is preferable that the olefin resin (β) further does not contain substances that cause coloring, off-flavor, and contamination of the final product. Specific examples of substances that cause the coloring, off-flavor, and contamination of the final product include heteroatom-containing compounds. Examples of the heteroatom-containing compound include a compound containing a halogen atom such as a chlorine atom and a bromine atom, a compound containing a chalcogen atom such as an oxygen atom and a sulfur atom, and a compound containing a pnictogen such as a nitrogen atom and a phosphorus atom. It is done. Specific examples of the compound containing an oxygen atom include maleic anhydride and a maleic anhydride reactant. Examples of substances that cause coloring, off-flavor and final product contamination include metal atom-containing compounds, specifically, alkali metal-containing compounds such as sodium and potassium, and alkaline earth metals such as magnesium and calcium. A metal containing compound is mentioned.

  1000 mass ppm or less is preferable, as for content of the said hetero atom containing compound of an olefin resin ((beta)), 100 mass ppm or less is more preferable, and 10 mass ppm or less is further more preferable. Moreover, 1000 mass ppm or less is preferable, as for content of the said metal atom containing compound of an olefin resin ((beta)), 100 mass ppm or less is more preferable, and 10 mass ppm or less is more preferable.

  The propylene-based resin composition according to the present invention can contain other resins, inorganic fillers such as rubber and talc, organic fillers and the like as long as the object of the present invention is not impaired. Further, the propylene-based resin composition according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, and an anti-aging agent. And additives such as a hydrochloric acid absorbent, an antioxidant, and a crystal nucleating agent. Content of said other resin, rubber | gum, an inorganic filler, an organic filler, an additive etc. will not be specifically limited if it is a range which does not impair the objective of this invention.

[Producing method of propylene-based resin composition]
The method for producing a propylene-based resin composition according to the present invention produces the olefin-based resin (β) by a method including the following steps (A) and (B).

(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process,
(B) In the presence of a catalyst for olefin polymerization containing a crosslinked metallocene compound represented by the following formula [B], the terminal unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms. A step of copolymerizing at least one α-olefin selected from the group consisting of:

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. And a group adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring, and R ⁶ and R ¹¹ are a hydrogen atom or a hydrocarbon. The same atom or the same group selected from the group consisting of a group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, and The same atom or the same group selected from the group consisting of heteroatom-containing groups other than silicon-containing groups R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ Are bonded together to form a ring Provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms, R ¹³ and R ¹⁴ each independently represents an aryl group, and Y ¹ represents a carbon atom or a silicon atom. M ¹ represents a zirconium atom or a hafnium atom, Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or A neutral ligand that can be coordinated by a lone pair of electrons, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. .

  Hereinafter, the step (A) and the step (B) will be described.

<Process (A)>
In the step (A), propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton, and terminal unsaturated polypropylene is obtained. Manufacturing. Step (A) is a step of producing terminal unsaturated polypropylene which is a raw material for a side chain composed of a propylene polymer of graft type olefin polymer [R1].

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

  The said transition metal compound [A] functions as a polymerization catalyst which manufactures terminal unsaturated polypropylene with the compound [C] mentioned later. Examples of olefin polymerization catalysts for producing terminally unsaturated polypropylene include Resconi, L., et al. As described in JACS 1992, 114, 1025-1032, etc., the side chain of the graft type olefin polymer [R1] is preferably isotactic or syndiotactic terminal unsaturated polypropylene, and is isotactic. Terminal unsaturated polypropylene is more preferred.

  Examples of the transition metal compound [A] contained in the olefin polymerization catalyst used for producing a polypropylene having such a high stereoregularity and a terminal unsaturated polypropylene content having a terminal structure (I) are high. It is disclosed in Kaihei 6-100579, JP 2001-525461 A, JP 2005-336091 A, JP 2009-299046 A, JP 11-130807 A, JP 2008-285443 A, etc. The compound which is mentioned.

  More specifically, the transition metal compound [A] is dimethylsilylbis (indenyl) zirconocene or hafnocene. More preferred is dimethylsilylbis (indenyl) zirconocene. By selecting zirconocene, the production of a long-chain branched polymer caused by the insertion reaction of terminal unsaturated polypropylene is suppressed, and the propylene-based resin composition containing the olefin-based resin (β) exhibits desired physical properties. On the other hand, when many said long chain branched polymers are produced | generated in a process (A), the propylene-type resin composition containing an olefin resin ((beta)) may impair physical properties, such as rigidity. As the transition metal compound [A], it is particularly preferable to use dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride or dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl. These may use 1 type and may use 2 or more types together.

  Step (A) can be carried out by any method of gas phase polymerization, slurry polymerization, bulk polymerization, and solution (dissolution) polymerization, and the polymerization form is not particularly limited. When the step (A) is performed by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used individually by 1 type or in combination of 2 or more types. Of these, hexane is preferred from the viewpoint of reducing the load of the post-treatment process.

  The polymerization temperature in the step (A) is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 150 ° C, and further preferably 80 ° C to 130 ° C. By controlling the polymerization temperature within the above range, a terminal unsaturated polypropylene having a desired molecular weight and stereoregularity can be obtained.

  The polymerization pressure in the step (A) is preferably normal pressure to 10 MPa gauge pressure, more preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. In the present invention, among these, a method in which a monomer is continuously supplied to a reactor to carry out copolymerization is preferable.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is preferably 0.5 minutes to 5 hours, and 5 minutes to 3 hours. More preferred.

  The polymer concentration in the step (A) is preferably 5 to 50% by mass and more preferably 10 to 40% by mass during steady operation. The polymer concentration is more preferably 15 to 40% by mass from the viewpoints of viscosity limitation in the polymerization ability, load of the post-treatment step (desolvation) and productivity.

  The weight average molecular weight of the terminal unsaturated polypropylene produced in the step (A) is preferably in the range of 5000 to 100,000, more preferably in the range of 5000 to 60000, and in the range of 5000 to 25000. More preferably. When the weight average molecular weight is within the above range, in the step (B) described later, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin, and introduced into the main chain. Increases efficiency. On the other hand, when the weight average molecular weight exceeds 100,000, the molar concentration of the terminal unsaturated polypropylene is relatively low, and the introduction efficiency into the main chain may be low. Moreover, when the weight average molecular weight is less than 5000, the melting point may be lowered.

  The molecular weight distribution (Mw / Mn) of the terminal unsaturated polypropylene produced in the step (A) is preferably 1.5 to 3.0, more preferably 1.7 to 2.5. It may be a mixture of side chains having different molecular weights.

The ratio of terminal unsaturation measured by ¹ H-NMR of the terminal unsaturated polypropylene produced in the step (A) is preferably 0.1 to 10.0 per 1000 carbon atoms, and is preferably 0.00. More preferably, the number is 4 to 5.0. Further, the proportion of terminal unsaturation having the terminal structure (I), the so-called terminal vinyl amount, is preferably 0.1 to 2.0 per 1000 carbon atoms, 0.4 to 2.0 More preferably. When the amount of terminal vinyl is small, the amount of terminal unsaturated polypropylene introduced into the main chain in the subsequent step (B) decreases, and the amount of graft-type olefin polymer [R1] produced decreases. The effect may not be obtained. Calculation of the amount of terminal unsaturation and the ratio of each terminal structure by ¹ H-NMR measurement can be performed according to the method described in Macromolecular Rapid Communications 2000, 1103, for example.

<Process (B)>
In the step (B), it is produced in the step (A) in the presence of an olefin polymerization catalyst containing a bridged metallocene compound represented by the formula [B] (hereinafter also referred to as a bridged metallocene compound [B]). The terminal unsaturated polypropylene, ethylene, and at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms are copolymerized.

  In the step (B), it is important to select a catalyst that exhibits sufficient activity at a high temperature, has high copolymerizability and can have a high molecular weight. Since the terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and has a sterically bulky structure, it is difficult to polymerize compared to a linear vinyl monomer. Moreover, terminal vinyl polypropylene is difficult to be copolymerized under low temperature conditions where the polymer is precipitated. For this reason, the catalyst is preferably required to exhibit a sufficient activity at a polymerization temperature of 90 ° C. or higher so that the main chain can have a desired molecular weight. From such a viewpoint, in the present invention, the bridged metallocene compound [B] is used in the step (B). The bridged metallocene compound [B] is selected from the group consisting of the terminal unsaturated polypropylene produced in the step (A), ethylene, and an α-olefin having 3 to 20 carbon atoms, together with the compound [C] described later. It functions as an olefin polymerization catalyst for copolymerizing at least one α-olefin.

  Hereinafter, the characteristics of the chemical structure of the bridged metallocene compound [B] used in the present invention will be described.

  The bridged metallocene compound [B] is structurally provided with the following features [m1] and [m2].

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

  [M2] The two ligands are bonded by an aryl group-containing covalently bonded bridge portion (hereinafter also referred to as “bridge portion”) composed of a carbon atom or silicon atom having an aryl group.

  Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the bridge | crosslinking part, and other characteristics which bridge | crosslinked metallocene compound [B] have are demonstrated sequentially.

(Cyclopentadienyl group which may have a substituent)
In the formula [B], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. From the viewpoint of satisfactorily incorporating terminal vinyl polypropylene, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R ¹ , R ² , R ³ and R ⁴ are methyl. It is preferably a group.

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

From the viewpoint of polymerization activity, R ⁶ and R ¹¹ are preferably not both hydrogen atoms, and R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are all preferably not hydrogen atoms, and R ⁶ and R ¹¹ are preferably More preferably, they are the same group selected from the group consisting of a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ are 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 are bonded to each other to form an alicyclic ring or an aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic ring or an aromatic ring.

Examples of the hydrocarbon group in R ^{5 to} R ¹² include a hydrocarbon group having 1 to 20 carbon atoms (hereinafter sometimes referred to as “hydrocarbon group (f1)”). Examples of the silicon-containing group in R ^{5 to} R ¹² include a silicon-containing group having 1 to 20 carbon atoms (hereinafter sometimes referred to as “silicon-containing group (f2)”). Examples of the heteroatom-containing group other than the silicon-containing group in R ^{5 to} R ¹² include heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups (excluding silicon-containing groups (f2)). .

  Specific examples of the hydrocarbon group (f1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, linear hydrocarbon group such as n-nonyl group, n-decanyl group, allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamanty group A cyclic saturated hydrocarbon group such as a group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group and a nuclear alkyl substituent thereof; a saturated hydrocarbon group such as a benzyl group and a cumyl group And a group in which at least one hydrogen atom of is substituted with an aryl group.

  Among the hydrocarbon groups (f1), a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group are more preferable.

  Examples of the silicon-containing group (f2) include a group in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group. Specifically, an alkylsilyl group (eg, trimethylsilyl group), aryl A silyl group (example: triphenylsilyl group) is mentioned.

  Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, and pentafluoroethyl. Group and pentafluorophenyl group.

The substituted fluorenyl group in the case where R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic ring or an aromatic ring is derived from the compounds represented by formulas [II] to [VI] described later. Are preferred.

(Bridged part)
In the formula [B], R ¹³ and R ¹⁴ each independently represents an aryl group, and Y ¹ represents a carbon atom or a silicon atom. An important point in the production of an olefin polymer is that the bridging atom Y ¹ of the bridging portion has R ¹³ and R ¹⁴ which are aryl groups which may be the same as or different from each other. From the standpoint of ease of production, R ¹³ and R ¹⁴ are preferably the same as each other.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of aromatic hydrogen (sp2-type hydrogen) contained in the aryl group is substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1), the silicon-containing group (f2), a halogen atom, and a halogenated hydrocarbon group.

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

(Other features of bridged metallocene compound [B])
In the formula [B], Q can be coordinated by a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a lone electron pair. A neutral ligand is shown, j shows an integer of 1-4, and when j is an integer greater than or equal to 2, some Q may be same or different, respectively.

  As a hydrocarbon group in Q, a C1-C10 linear or branched aliphatic hydrocarbon group and a C3-C10 alicyclic hydrocarbon group are mentioned, for example. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -A trimethylbutyl group and a neopentyl group are mentioned. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

  Examples of the halogenated hydrocarbon group for Q include groups in which at least one hydrogen atom of the hydrocarbon group for Q is substituted with a halogen atom.

In the formula [B], M ¹ represents a zirconium atom or a hafnium atom. M ¹ is preferably a hafnium atom from the viewpoint of copolymerizing terminal unsaturated polypropylene with high efficiency and controlling the molecular weight. The use of a catalyst having a performance capable of copolymerizing terminally unsaturated polypropylene with high efficiency and controllable to a high molecular weight is important for ensuring high productivity. This is because it is desirable to carry out the reaction under high temperature conditions in order to ensure high productivity, but the molecular weight produced tends to decrease under high temperature conditions.

(Example of preferred bridged metallocene compound [B])
Specific examples of the bridged metallocene compound [B] are shown below. In the exemplary compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the following formula [II]. Octamethyltetrahydrodicyclopentafluorenyl is a group derived from a compound having a structure represented by the following formula [III]. Dibenzofluorenyl is a group derived from a compound having a structure represented by the following formula [IV]. 1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl is a group derived from a compound having a structure represented by the following formula [V]. 1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl is a group derived from a compound having a structure represented by the following formula [VI].

  As such a bridged metallocene compound [B], di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride is used in the examples described later. The bridged metallocene compound [B] is not limited to this compound, and all bridged metallocene compounds exemplified in International Publication No. 2005/100410 can be used without limitation.

  The bridged metallocene compound [B] can be produced by a known method. Known methods include, for example, the methods described in WO 01/27124 and WO 04/029062.

  The bridged metallocene compound [B] can be used alone or in combination of two or more.

  Step (B) can be carried out in solution (dissolution) polymerization. In particular, the step (B) is preferably a solution polymerization step in which copolymerization is performed at 90 ° C. or higher. Although it will not specifically limit if the polymerization method for manufacturing an olefin type polymer is used about a polymerization method, It is preferable to have the process of obtaining the following polymerization reaction liquid.

The step of obtaining a polymerization reaction liquid is a method in which an aliphatic hydrocarbon is used as a polymerization solvent, and R ¹³ and R ¹⁴ bonded to the bridged metallocene compound [B], preferably Y ¹ in the formula [B] are phenyl groups. Or a phenyl group substituted with an alkyl group or a halogen group, and in the presence of a metallocene catalyst containing a compound in which R ⁷ and R ¹⁰ are alkyl substituents, ethylene and an α-olefin having 3 to 20 carbon atoms And a step of obtaining a polymerization reaction solution of a copolymer with the terminal unsaturated polypropylene produced in the step (A).

  In step (B), the terminal unsaturated polypropylene produced in step (A) is fed to the reactor in step (B) in the form of a solution or slurry. The feeding method is not particularly limited. Even if the polymerization solution obtained in step (A) is continuously fed to the reactor in step (B), the polymerization solution in step (A) is temporarily buffered. You may feed to a process (B), after storing in a tank.

  Examples of the polymerization solvent in the step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used individually by 1 type or in combination of 2 or more types. Further, the polymerization solvent in step (B) may be the same as or different from the polymerization solvent in step (A). Of these, aliphatic hydrocarbons such as hexane and heptane are preferable from the industrial viewpoint, and hexane is more preferable from the viewpoint of separation and purification from the olefin resin (β).

  90 degreeC-200 degreeC is preferable and, as for the polymerization temperature of a process (B), 100 degreeC-200 degreeC is more preferable. In aliphatic hydrocarbons such as hexane and heptane that are preferably used industrially as the polymerization solvent, the temperature at which the terminal unsaturated polypropylene is satisfactorily dissolved is 90 ° C. or higher, and therefore the polymerization temperature is 90 ° C. or higher. Is preferred. Moreover, it is preferable that the polymerization temperature is higher from the viewpoint of improving the introduction amount of polypropylene side chains and improving productivity.

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

  The reaction time in step (B) (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but preferably 0.5 minutes to 5 hours. Minute to 3 hours are more preferable.

  The polymer concentration in the step (B) is preferably 5 to 50% by mass and more preferably 10 to 40% by mass during steady operation. From the viewpoints of viscosity limitation in polymerization ability, post-treatment process (desolvation) load, and productivity, the content is more preferably 15 to 35% by mass.

  The molecular weight of the resulting copolymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the usage-amount of compound [C1] mentioned later. Specific examples of the compound [C1] include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount of hydrogen added is preferably 0.001 to 100 NL per kg of olefin.

<Compound [C]>
In the step (A) and the step (B), it is preferable to use the compound [C] together with the transition metal compound [A] and the bridged metallocene compound [B] used as the olefin polymerization catalyst.

  Compound [C] functions as a catalyst for olefin polymerization by reacting with transition metal compound [A] and bridged metallocene compound [B]. As the compound [C], specifically, [C1] an organometallic compound, [C2] an organoaluminum oxy compound, and [C3] a transition metal compound [A] or a bridged metallocene compound [B] react with ions. Compounds that form a pair are listed. Hereinafter, the compounds [C1] to [C3] will be sequentially described.

([C1] organometallic compound)
[C1] Specific examples of the organometallic compound include an organoaluminum compound represented by the following formula (C1-a), a complex of a group 1 metal of the periodic table represented by the following formula (C1-b) and aluminum. Examples thereof include alkylated products and dialkyl compounds of Group 2 or Group 12 metals represented by the following formula (C1-c). Note that the [C1] organometallic compound does not include the [C2] organoaluminum oxy compound described later.

^{_{R a p Al (OR b)}} q H r Y s (C1-a)
In the formula (C1-a), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom. p is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and p + q + r + s = 3.

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

R ^d R ^e M ⁴ (C1-c)
In the formula (C1-c), R ^d and R ^e each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M ⁴ is Mg, Zn or Cd.

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

R ^a _p Al (OR ^b ) _3-p (C-1a-1)
In the formula (C-1a-1), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. p is 1.5 ≦ p ≦ 3.

R ^a _p AlY _3-p (C-1a-2)
In the formula (C-1a-2), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom. p is 0 <p <3.

R ^a _p AlH _3-p (C-1a-3)
In the formula (C-1a-3), R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. p is 2 ≦ p <3.

^{_{R a p Al (OR b)}} q Y s (C-1a-4)
In the formula (C-1a-4), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom. p is 0 <p ≦ 3, q is 0 ≦ q <3, s is 0 ≦ s <3, and p + q + s = 3.

Specific examples of the organoaluminum compound represented by the formula (C1-a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, and tripropylaluminum;
Tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x) tri isoprenylaluminum represented by etc. Of trialkenylaluminum;
Alkyl aluminum alkoxides of isobutyl aluminum methoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b are each independently from 1 to 15 carbon atoms) , Preferably a C 1-4 hydrocarbon group);
Dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to the organoaluminum compound represented by the formula (C1-a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound represented by the formula (C1-b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound represented by the formula (C1-c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n. -Butyl zinc, dimethyl cadmium, diethyl cadmium, etc. can be mentioned.

  In addition, methyllithium, ethyllithium, propyllithium, butyllithium, and the like can also be used as the [C1] organometallic compound.

  In addition, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium is used as the [C1] organometallic compound. You can also

  These [C1] organometallic compounds can be used singly or in combination of two or more.

([C2] organoaluminum oxy compound)
[C2] The organoaluminum oxy compound may be a known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. [C2] Specific examples of the organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.

The known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

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

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the formula (C1-a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is more preferable. These organoaluminum compounds can be used alone or in combination of two or more.

  Solvents used for the preparation of the aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, cyclohexane. Aliphatic hydrocarbons such as pentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or the aromatic hydrocarbons, halides of the aliphatic hydrocarbons and the alicyclic hydrocarbons Among others, hydrocarbon solvents such as chlorinated products and brominated products can be mentioned. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are preferred. These solvents may be used alone or in combination of two or more.

  In the benzene-insoluble organoaluminum oxy compound, the Al component dissolved in benzene at 60 ° C. is preferably 10% or less, more preferably 5% or less, and more preferably 2% or less in terms of Al atoms. Further preferred. That is, the benzene-insoluble organoaluminum oxy compound is preferably insoluble or hardly soluble in benzene.

  [C2] Examples of the organoaluminum oxy compound include an organoaluminum oxy compound containing boron represented by the following formula (III).

In the formula ^{(III), R 17} represents a hydrocarbon group having 1 to 10 carbon atoms. Four R ¹⁸ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

  The organoaluminum oxy compound containing boron represented by the formula (III) includes, for example, an alkyl boronic acid represented by the following formula (IV) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. , And can be produced by reacting at -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁹ -B (OH) ₂ (IV)
In the formula (IV), R ¹⁹ has the same meaning as R ¹⁷ in the formula (III).

  Specific examples of the alkyl boronic acid represented by the formula (IV) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boronic acid, cyclohexyl. Examples thereof include boronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These can be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the formula (C1-a). As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferable. These can be used alone or in combination of two or more.

  The said [C2] organoaluminum oxy compound can be used individually by 1 type or in combination of 2 or more types.

([C3] Compound that reacts with transition metal compound [A] or bridged metallocene compound [B] to form an ion pair)
JP-A-1-501950 discloses a compound that forms an ion pair by reacting with the [C3] transition metal compound [A] or the bridged metallocene compound [B] (hereinafter referred to as “[C3] ionized ionic compound”). JP, 1-502036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Examples of the Lewis acid include a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group). Specifically, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron Etc.

  Examples of the ionic compound include compounds represented by the following formula (V).

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

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

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

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

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

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

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

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

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

  Furthermore, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbe Examples thereof include a nium pentaphenylcyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VI) or (VII).

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

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

  [C3] Specific examples of the borane compound as an example of the ionized ionic compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like. Salts; salts of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III).

  [C3] Specific examples of carborane compounds that are examples of ionized ionic compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, and the like. Can be used without limitation.

  [C3] The heteropoly compound, which is an example of the ionized ionic compound, includes at least one atom selected from the group consisting of silicon, phosphorus, titanium, germanium, arsenic, and tin, and a group consisting of vanadium, niobium, molybdenum, and tungsten. A compound containing at least one selected atom. Specific examples of the heteropoly compound include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic acid, and salts of these acids. It is done. The salt includes, for example, metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and the like. And organic salts such as triphenylethyl salt.

  [C3] An isopoly compound, which is an example of an ionized ionic compound, is a compound composed of a metal ion of at least one atom selected from the group consisting of vanadium, niobium, molybdenum, and tungsten. It can be regarded as an ionic species. Specific examples of the isopoly compound include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. In addition, the salt includes, for example, a metal of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and the like. Examples thereof include organic salts such as salts and triphenylethyl salts.

  The said [C3] ionized ionic compound can be used individually by 1 type or in combination of 2 or more types.

  [C1] The organometallic compound has a molar ratio (C1 / M) between the [C1] organometallic compound and the transition metal atom (M) in the transition metal compound [A] in the step (A). ), The molar ratio (C1 / M) with the transition metal atom (M) in the bridged metallocene compound [B] is preferably 0.01 to 100,000, more preferably 0.05 to 50,000. be able to.

  [C2] The organoaluminum oxy compound is a molar ratio (C2 / M) of the aluminum atom in the [C2] organoaluminum oxy compound and the transition metal atom (M) in the transition metal compound [A] in the step (A). However, in the step (B), the molar ratio (C2 / M) with the transition metal atom (M) in the bridged metallocene compound [B] is preferably 10 to 500,000, more preferably 20 to 100,000. Can be used.

  [C3] The ionized ionic compound has a molar ratio (C3 / M) of [C3] ionized ionic compound to transition metal atom (M) in transition metal compound [A] in step (A). In (B), the molar ratio (C3 / M) with the transition metal atom (M) in the bridged metallocene compound [B] is preferably 1 to 10, more preferably 1 to 5. it can.

  In particular, when a [C2] organoaluminum oxy compound such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound [A] and the bridged metallocene compound [B], high polymerization activity is exhibited with respect to the olefin compound.

<Process (C)>
In the present invention, in the production of the olefin resin (β), in addition to the step (A) and the step (B), a step (C) of recovering the polymer produced in the step (B) as necessary. May be implemented. This step is a step of separating the organic solvent used in the step (A) and the step (B), taking out the polymer, and converting it into a product form. The existing polyolefin such as solvent concentration, extrusion degassing, pelletizing, etc. If it is the process of manufacturing resin, there will be no restriction | limiting in particular.

  In the propylene-based resin composition according to the present invention, at least the propylene-based resin (α) and the olefin-based resin (β) are mixed at a predetermined blending ratio by a melting method, a solution method, or the like, preferably a melt-kneading method. Can be obtained. As the melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. The propylene-based resin composition is, for example, pulverized or granular components, together with other additives as necessary, uniformly mixed with a Henschel mixer, ribbon blender, V-type blender, etc. It can be prepared by kneading with a kneading extruder, kneading roll, batch kneader, kneader, Banbury mixer or the like. 170-250 degreeC is preferable and, as for the melt-kneading temperature (for example, cylinder temperature in the case of an extruder) of each component, 180-230 degreeC is more preferable. The kneading order and kneading method of each component are not particularly limited.

[Molded body]
The molded body according to the present invention is a molded body of the propylene-based resin composition according to the present invention. The propylene-based resin composition according to the present invention can improve impact resistance while maintaining rigidity, and has an excellent balance between rigidity and impact resistance. Therefore, injection molding, extrusion molding, inflation molding, blow molding It can be molded into various molded articles by known molding methods such as extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. The molded body according to the present invention can be applied to various known uses such as automobile parts, containers for food use and medical use, and packaging materials for food use and electronic materials. Moreover, this molded object is applicable also to a film, a sheet | seat, a tape, and other uses.

  The molded body according to the present invention is excellent in the balance between rigidity and impact resistance, has a high surface hardness, and is excellent in chemical resistance. Therefore, it can be used for various automobile parts. The molded body includes, for example, automotive exterior parts such as bumpers, side moldings, and aerodynamic undercovers, automotive interior parts such as instrument panels and interior trims, outer panel parts such as fenders, door panels, and steps, engine covers, fans, and fans. It can be used for engine surrounding parts such as a shroud.

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

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

  Films, sheets, and tapes include, for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical components, protective films for lenses, protective films for electrical components and electrical appliances, protective films for mobile phones, and for personal computers. Examples of the protective film include a protective film, a masking film, a capacitor film, a reflective film, a laminate (including glass), a radiation resistant film, a γ-ray resistant film, and a porous film.

  Other uses include, for example, housings for home appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, cosmetic / perfume spray tubes, medical tubes, infusion tubes, pipes, wire harnesses, motorcycles / railways Interior materials for vehicles, aircraft, ships, etc., instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, armrest, airbag case lid, shift knob, assist grip, side step Mat, reclining cover, trunk seat, seat belt buckle, inner / outer molding, roof molding, belt molding and other molding materials, door seals, body sealing and other automotive sealing materials, glass run channels, mudguards, Automotive interior and exterior materials such as a rocking plate, step mat, license plate housing, automotive hose member, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, bonnet cushion, door cushion, damping tire, Special tires such as static tires, car race tires, radio control tires, packing, automotive dust covers, lamp seals, automotive boot materials, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, furniture / Skin materials for footwear, clothing, bags, building materials, etc., sealing materials for construction, waterproof sheets, building material sheets, gaskets for building materials, window films for building materials, iron core protection members, gaskets, doors, door frames, window frames, peripheral edges Baseboard, opening frame, flooring, ceiling material, wallpaper, health supplies (eg, non-slip mats / sheets, anti-tip films / mats / sheets), health equipment components, shock absorbing pads, protectors / protectors (eg: Helmets, guards), sports equipment (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, transportation equipment (eg transportation shock absorbing grips, shock absorbing sheets), damping pallets Shock absorbers, insulators, shock absorbers for footwear, shock absorbing foams, shock absorbing materials such as shock absorbing films, grip materials, miscellaneous goods, toys, shoe soles, shoe soles, shoe midsole / inner soles, soles , Sandals, suckers, toothbrushes, flooring materials, gymnastic mats, power tool members, agricultural equipment members, heat dissipation materials, transparent substrates, soundproofing materials, cushions After filling the bottle with baby food, dairy products, pharmaceuticals, sterilized water, etc., heat treatment such as boiling and high-pressure steam sterilization Packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as plastic bottle cap liners, stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, audio Precision equipment such as anti-vibration materials, OA equipment supporting members, OA heat-resistant packing, animal cages, beakers, measuring cylinders, physics and chemistry laboratory equipment, optical measurement cells, costume cases, clear cases, clear files, clear sheets, desk mats For use as a fiber, for example, non-woven fabric, stretchable non-woven fabric , 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, the molded body according to the present invention can improve impact resistance while maintaining rigidity, and has an excellent balance between rigidity and impact resistance, so that it is particularly useful in automobiles such as bumpers and instrument panels. It can be suitably used for exterior materials, outer plate materials, food containers, and beverage containers.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.

  In the following examples, the physical properties of the olefin resin (β), terminal unsaturated polypropylene, propylene resin (α), and propylene resin composition were measured by the following methods.

(1) Measurement of melting point (Tm) and heat of fusion ΔH The melting point (Tm) and heat of fusion ΔH were measured by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC220, company SII), a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere and held at that temperature for 10 minutes. did. Further, the temperature was lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then heated to 200 ° C. at a temperature raising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was defined as the melting peak, and the temperature at which the melting peak appears was determined as the melting point (Tm). The heat of fusion ΔH was determined by calculating the area of the melting peak. When the melting peak was multimodal, the area of the entire melting peak was calculated.

(2) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) was measured by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC220, company SII), a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere and held at that temperature for 10 minutes. did. Further, after cooling to −100 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The glass transition temperature (Tg) is sensed in such a manner that the DSC curve is bent due to the change in specific heat and the base line moves in parallel during the second temperature increase. The glass transition temperature (Tg) was defined as the temperature at the intersection of the tangent to the base line, which is lower than the bending, and the tangent at the point where the inclination is maximum at the bent portion.

(3) Measurement of insoluble amount of hot xylene The sample was formed into a sheet having a thickness of 0.4 mm by hot pressing (180 ° C., heating 5 minutes—cooling 1 minute) and finely cut. About 100 mg was weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a sealed container. Next, the screen was taken out and dried at 80 ° C. until a constant weight was obtained for 2 hours or more. The amount of hot xylene insoluble (mass%) was calculated by the following formula.

Thermal xylene insoluble amount (% by mass) = 100 × (W3-W2) / (W1-W2)
W1: Screen and sample mass before test, W2: Screen mass, W3: Screen and sample mass after test.

(4) Proportion P of propylene polymer contained in olefin resin (β)
The ratio P was calculated from the ratio of the mass of the terminal unsaturated polypropylene used in the step (B) and the mass of the obtained olefin resin (β).

(5) Cross-fractionation chromatograph (CFC) measurement Olefin resin (β) having a component with a differential elution curve peak value of less than 65 ° C. measured by cross-fractionation chromatography (CFC) using orthodichlorobenzene as a solvent. The calculation method of the ratio E with respect to is as follows.

Apparatus: Cross fractionation chromatograph CFC2 (Polymer ChAR)
Detector (built-in): Infrared spectrophotometer IR ⁴ (Polymer ChAR)
Detection wavelength: 3.42 μm (2,920 cm ⁻¹ ); fixed Sample concentration: 120 mg / 30 mL
Injection volume: 0.5 mL
Temperature drop time: 1.0 ° C / min
Elution category: 4.0 ° C intervals (-20 ° C to 140 ° C)
GPC column: Shodex HT-806M x 3 (trade name, manufactured by Showa Denko KK)
GPC column temperature: 140 ° C
GPC column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
Molecular weight calibration method: General-purpose calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (with BHT added)
Flow rate: 1.0 mL / min.

In calculating the ratio E, the differential elution curve obtained by the CFC measurement is peak-separated by a normal distribution curve, and the sum E _{(> 65 ° C.)} of the ratio (mass%) of the elution component having a peak temperature of 65 ° C. or higher is obtained. , E = 100−E _{(> 65 ° C.)} .

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

    [Η] = lim (ηsp / C) (C → 0).

(7) ¹³ C-NMR measurement For the purpose of confirming the composition ratio analysis of the ethylene and α-olefin of the polymer and the stereoregularity of the terminal unsaturated polypropylene, ¹³ C-NMR measurement was performed under the following conditions.

Apparatus: AVANCEIII500 CryoProbe Prodigy type nuclear magnetic resonance apparatus (trade name, manufactured by Bruker BioSpin)
Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 microseconds)
Number of points: 64k
Measurement range: 250 ppm (-55 to 195 ppm)
Repeat time: 5.5 seconds Integration count: 512 times Measurement solvent: orthodichlorobenzene / benzene-d ₆ (4/1 v / v)
Sample concentration: ca. 60mg / 0.6mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 1.0 Hz)
Chemical shift criteria: benzene-d ₆ (128.0 ppm).

(8) ¹ H-NMR measurement In order to analyze the terminal structure of the terminal unsaturated polypropylene, ¹ H-NMR measurement was performed under the following conditions.

Apparatus: ECX400P nuclear magnetic resonance apparatus (trade name: manufactured by JEOL Ltd.)
Measurements ^nuclear: 13 H (400MHz)
Measurement mode: Single pulse Pulse width: 45 ° (5.25 μsec)
Number of points: 32k
Measurement range: 20 ppm (-4 to 16 ppm)
Repeat time: 5.5 seconds Integration count: 64 times Measurement solvent: 1,1,2,2, -tetrachloroethane-d2
Sample concentration: ca. 60mg / 0.6mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 0.12 Hz)
Chemical shift criteria: 1,1,2,2, -tetrachloroethane (5.91 ppm).

(9) GPC measurement For molecular weight analysis of the polymer, GPC measurement was carried out under the following conditions.

Apparatus: Alliance GPC 2000 type (trade name, manufactured by Waters)
Column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (trade name, all manufactured by Tosoh Corporation, inner diameter 7.5 mm × length 30 cm)
Column temperature: 140 ° C
Mobile phase: orthodichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: differential refractometer Flow rate: 1.0 mL / min Sample concentration: 0.15% (w / v)
Injection volume: 0.5 mL
Sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).

(10) Measurement of melt flow rate (MFR (g / 10 min)) The melt flow rate was measured with a 2.16 kg load in accordance with ASTM D1238E. The measurement temperature was 230 ° C.

(11) Measurement of isotactic pentad fraction (mmmm (%)) One of the indexes of the stereoregularity of the polymer, the pentad fraction (mmmm (%)) of which the microtacticity was examined is It calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Macromolecules 8,687 (1975) in the propylene-based resin (α). ^{The 13} C-NMR spectrum was measured using EX-400 (trade name, manufactured by JEOL Ltd.) as an apparatus, using TMS as a reference, and a temperature of 130 ° C. and an o-dichlorobenzene solvent. The isotactic pentad fraction was measured for terminally unsaturated polypropylene M-2.

(12) Measurement of ratio of units derived from ethylene 20 to 30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (mass ratio: 2/1) solution, followed by carbon nuclear magnetic resonance analysis ( ¹³ C-NMR). Propylene and ethylene were quantitatively determined from the dyad chain distribution. In the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, and EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ were used, and the following formula was used.

    Ratio of units derived from ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)].

(13) Measurement of flexural modulus (FM (MPa)) The flexural modulus was measured under the following conditions in accordance with JIS K7171.

Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm.

(14) Measurement of Charpy impact strength A Charpy impact test was performed under the following conditions in accordance with JIS K7111, and Charpy impact strength (kJ / m ² ) was measured.

Temperature: -30 ° C, 23 ° C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness).

  The notch is machined.

(Reagent used)
Toluene was purified using an organic solvent purifier manufactured by GlassContour. As a toluene solution of aluminoxane, a 20 mass% methylaluminoxane / toluene solution manufactured by Nippon Alkyl Aluminum Co. was used. Triisobutylaluminum manufactured by Tosoh Finechem Corporation was diluted with toluene (1.0 mol / L).

[Production Example 1]
Step (A): Production of terminal unsaturated polypropylene (M-2) To a 1 L stainless steel autoclave thoroughly purged with nitrogen, 500 mL of toluene and a toluene solution of methylaluminoxane (1.5 mol / L) 0 under nitrogen flow .67 mL (1.0 mmol) was added. Thereafter, the autoclave was closed and the temperature was raised to 85 ° C. Next, the propylene partial pressure was increased to 0.3 MPa while stirring the interior of the polymerization vessel at 600 rpm, and then maintained at 85 ° C. Therein, 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol / L) of dimethylsilylbis (2-methyl-4-finylindenyl) zirconium dichloride was injected to initiate polymerization. The pressure was maintained while continuously supplying propylene gas, and the polymerization was carried out at 85 ° C. for 20 minutes, and then the polymerization was stopped by injecting 5 mL of methanol. The obtained polymerization reaction liquid was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours to obtain 14.9 g of terminal unsaturated polypropylene (M-2). Table 2 shows the analysis results of the obtained polymer.

Step (B): Production of Olefin Resin (β-1) After putting 10.0 g of the terminal unsaturated polypropylene (M-2) and 500 ml of xylene into a 1 L glass reactor sufficiently purged with nitrogen. The temperature was raised to 97 ° C. to dissolve the terminal unsaturated polypropylene (M-2). While stirring the inside of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously supplied at 120 liter / hr and 20.4 liter / hr, respectively, to saturate the liquid phase and the gas phase. Subsequently, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al) in a state where ethylene and 1-butene are continuously supplied is represented by the following formula. Toluene solution of compound in toluene (0.0020 mol / L) followed by 5.0 mL (0.01 mmol) followed by triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) 6.25 mL (0.025 mmol) was added (4.0 mmol / L), and polymerization was performed at 97 ° C. for 40 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 35.2 g of an olefin resin (β-1). The compound represented by the following formula used as a catalyst was synthesized by a known method. The analysis results of the olefin resin (β-1) are shown in Table 1.

[Production Example 2]
Production of Olefin Resin (β′-1) Olefin resin (β′-1) was produced in the same manner as in Production Example 1 except that the step (B) was carried out without adding the terminal unsaturated polypropylene (M-2). 1) was produced. 21.4 g of olefin resin (β′-1) was obtained. Table 1 shows the analysis results of the olefin resin (β′-1).

[Production Example 3]
Production of Olefin Resin (β′-2) Olefin Resin (β′-2) was produced in the same manner as in Production Example 1 except that the step (B) was carried out by changing the supply amount of 1-butene to 15 l / hr. -2) was produced. 31.4g of olefin resin ((beta) '-2) was obtained. Table 1 shows the analysis result of the olefin resin (β′-2).

[Production Example 4]
Production of propylene-based homopolymer resin (α-h-1) (1) Preparation of solid titanium catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours. To obtain a homogeneous solution. 21.3 g of phthalic anhydride was added to the solution, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

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

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

Here, the free titanium compound was detected by the following method. 10 ml of the washing solution of the solid titanium catalyst component was collected with a syringe and placed in a 100 ml branch schlenk previously purged with nitrogen. Next, hexane was dried under a nitrogen stream and further vacuum-dried for 30 minutes. To this, 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were added and stirred for 30 minutes. This aqueous solution is passed through a filter paper and transferred to a 100 ml volumetric flask. Subsequently, 1 ml of concentrated H ₃ PO ₄ as a masking agent for iron (II) ions and 5 ml of 3% H ₂ O ₂ as a coloring agent for titanium are added, and ion-exchanged water is used. The volume was 100 ml. The volumetric flask was shaken and after 20 minutes, absorbance at 420 nm was observed using a UV measuring device. The free titanium was washed away until this absorption was not observed.

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

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

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

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

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

[Example 1]
23 parts by mass of the olefin resin (β-1) produced in Production Example 1, 57 parts by mass of the propylene homopolymer resin (α-h-1) produced in Production Example 4, talc (trade name: JM- 209, manufactured by Asada Flour Milling Co., Ltd.) 20 parts by mass, heat resistance stabilizer IRGANOX 1010 (trade name, manufactured by Ciba Geigy Co., Ltd.) 0.1 part by mass, heat resistance stabilizer IRGAFOS 168 (trade name, manufactured by Ciba Geigy Co., Ltd.) 0.1 After mixing parts by mass and 0.1 parts by mass of calcium stearate with a tumbler, the mixture was melt-kneaded with a twin screw extruder under the following conditions to prepare a pellet-shaped propylene resin composition. Using the pellet-shaped propylene-based resin composition, an injection molding machine was used for injection molding under the following conditions to prepare a test piece. Table 3 shows the physical properties of the resulting propylene-based resin composition.

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

[Example 2]
23 parts by mass of the olefin resin (β-1) produced in Production Example 1 was changed to 20 parts by mass, and 57 parts by mass of the propylene homopolymer resin (α-h-1) produced in Production Example 4 was changed. A propylene-based resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 60 parts by mass. Table 3 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 1]
Example 1 except that 23 parts by mass of the olefin resin (β′-1) produced in Production Example 2 was used instead of 23 parts by mass of the olefin resin (β-1) produced in Production Example 1. A propylene-based resin composition was prepared in the same manner as described above. Table 3 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 2]
A propylene resin composition was prepared in the same manner as in Comparative Example 1, except that 23 parts by mass of the olefin resin (β′-1) produced in Production Example 2 was changed to 26 parts by mass. Table 3 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 3]
Example 1 except that 20 parts by mass of the olefin resin (β′-2) produced in Production Example 3 was used instead of 23 parts by mass of the olefin resin (β-1) produced in Production Example 1. A propylene-based resin composition was prepared in the same manner as described above. Table 3 shows the physical properties of the resulting propylene-based resin composition.

[Comparative Example 4]
A propylene resin composition was prepared in the same manner as in Comparative Example 3, except that 20 parts by mass of the olefin resin (β′-2) produced in Production Example 3 was changed to 23 parts by mass. Table 3 shows the physical properties of the resulting propylene-based resin composition.

  In Table 3, the values in parentheses in the olefin resin and the propylene resin are the mass parts of the olefin resin or the propylene resin when the total of the olefin resin and the propylene resin is 100 parts by mass. Each is shown.

Claims (8)

2-50 parts by mass of an olefin resin (β) satisfying the following requirements (I) to (VI) other than 50 to 98 parts by mass of the propylene resin (α) and the propylene resin (α) (the propylene resin (α ) And the olefin resin (β) is 100 parts by mass).
(I) The olefin resin (β) includes a graft olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer.
(II) When the ratio of the propylene polymer contained in the olefin resin (β) is P mass%, P is in the range of more than 20 and 60 or less.
(III) The proportion of the component having a differential elution curve peak value of less than 65 ° C. measured by a cross-fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent to the olefin resin (β) is expressed as E mass%. The value a represented by the following formula (Eq-1) is 1.4 or more.
a = (100-E) / P (Eq-1)
(IV) Melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C, and glass transition temperature (Tg) is in the range of -80.0 to -30.0 ° C. is there.
(V) The thermal xylene insoluble amount is 3% by mass or less.
(VI) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 1.8 dl / g.   The proportion of ethylene-derived units contained in the olefin resin (β) is in the range of 20 to 80 mol% with respect to units derived from all monomers contained in the olefin resin (β). Resin composition.   The propylene-based resin composition according to claim 1 or 2, wherein an isotactic pentad fraction (mmmm) of the propylene polymer constituting a side chain of the graft-type olefin polymer [R1] is 93% or more. object.   The propylene-based resin composition according to any one of claims 1 to 3, wherein a weight average molecular weight of the propylene polymer constituting the side chain of the graft-type olefin-based polymer [R1] is within a range of 5,000 to 100,000. .   5. The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] is in the range of 50,000 to 200,000. 5. Propylene-based resin composition. A method for producing the propylene-based resin composition according to any one of claims 1 to 5,
The manufacturing method of the propylene-type resin composition which manufactures the said olefin resin ((beta)) with the method of including the following process (A) and process (B).
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Process,
(B) In the presence of a catalyst for olefin polymerization containing a crosslinked metallocene compound represented by the following formula [B], the terminal unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms. A step of copolymerizing at least one α-olefin selected from the group consisting of:

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. And a group adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group.
R ⁷ and R ¹⁰ 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 heteroatom-containing group other than a silicon-containing group.
R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represents an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )   The method for producing a propylene-based resin composition according to claim 6, wherein the step (B) is a solution polymerization step in which copolymerization is performed at 90 ° C. or higher.   The molded object of the propylene-type resin composition in any one of Claims 1-5.

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