JP6514617B2 - Propylene-based resin composition, method for producing the same, and molded body - Google Patents

Description

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

  Among olefin resins, propylene resin is used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electric parts, automobile parts, etc., and variously according to required performance. A propylene-based resin composition in which the following additives are blended is used. In addition, as efforts to 3R (Reduce, Reuse, Recycle) to form a recycling society, weight reduction by thin-walled molded articles has recently been attempted in each industrial field. Improvements in propylene-based resin compositions have been advanced so that sufficient rigidity and impact resistance can be obtained even if the molded article is reduced in weight and thickness.

  Polypropylene block copolymers are industrially produced as impact-modified polypropylene and are widely used in the aforementioned applications. This block copolymer is also called an impact copolymer or heterophase copolymer. That is, in the multistage polymerization process, following polymerization of the homopolymer, ethylene is copolymerized in a subsequent reaction vessel to produce a composition containing an ethylene-propylene polymer. The block copolymer thus produced has a structure (sea-island structure) in which the “island” of the ethylene-propylene polymer floats in the “sea” of the homopolymer, so it is more resistant to propylene homopolymers. Excellent impact strength. The term "block" of this polypropylene block copolymer does not mean "block copolymer". That is, the polypropylene block copolymer does not mean that the homopolypropylene chain and the ethylene-propylene copolymer chain are chemically bonded, but 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 a component having a low ethylene content and a component having a high content of ethylene-propylene copolymer rubber are present A propylene-based resin composition comprising a material is disclosed. Patent Document 2 discloses a propylene block copolymer-based 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 the request for further increasing the rigidity.

  On the other hand, Patent Document 3 discloses a technique of performing multi-stage polymerization with a catalyst containing a crosslinked bis indenyl zirconocene which generates a vinyl group at an end. In the technique of Patent Document 3, by polymerizing propylene in the former stage, and copolymerizing some comonomers and polypropylene in the latter stage, a part of the polypropylene having a vinyl structure at the end formed in the former stage becomes the main chain in the latter stage polymerization. It is captured. As a result, a composition containing a branched propylene copolymer in which polypropylene is grafted is obtained. Further, Patent Document 4 and Patent Document 5 disclose a technique for obtaining a branched polymer having a higher molecular weight of side chain polypropylene by using a cross-linked bis-indenyl hafnocene complex-supported catalyst system. Unlike the block copolymers, the techniques of Patent Documents 3 to 5 partially have branched polymers. Due to the presence of the branched polymer, the compatibility between the polypropylene portion and the rubber portion is enhanced, and a polypropylene composition having characteristics of excellent transparency and high melting property can be obtained. However, the techniques of Patent Documents 3 to 5 can not sufficiently increase the melting point of the polypropylene part compared to the above-mentioned polypropylene block copolymer obtained by a general-purpose Ziegler-Natta catalyst system, and limit the comonomer composition and molecular weight of the rubber part. However, it has not been possible to provide a polypropylene resin composition that sufficiently achieves rigidity and impact resistance.

  From such a background, the technological development of block polymers (including linear type and branched type), which is excellent in polypropylene resin modification performance and in which an ethylene copolymer and polypropylene are combined, has been advanced.

  In Patent Document 6 and Patent Document 7, reactive functional groups such as maleic acid, halogen and releasable metal are introduced into polyolefin, and ethylene / α-olefin copolymer chain and crystalline propylene polymer chain are cupped. A method of obtaining a high content of the target polymer composition by ring reaction is disclosed. However, in this method, the reaction steps such as introduction of functional groups to the polymer and coupling steps are complicated and inferior in productivity, and coloring and offensive odor due to byproducts and residual substrates generated in each reaction step and contamination due to eluting components It may occur.

  Patent Document 8 discloses a method of obtaining a linear block copolymer composed of 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 the application is limited. On the other hand, there is also disclosed a method of economically obtaining a branched copolymer of an ethylene copolymer and polypropylene by using a polymerization catalyst technology. For example, in Patent Document 9 and Patent Document 10, 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, and Patent Document 10 uses a specific polymerization catalyst and is excellent as a thermoplastic elastomer such as elastic recovery rate. Disclosed is a composition comprising a grafted olefin polymer having a crystalline propylene polymer as a side chain, characterized in that it exhibits physical properties.

  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, in the disclosed technology, the generation efficiency of the grafted olefin polymer is When it is low and it mix | blends with a polypropylene resin and it is set as a composition, improvement of a physical-property balance is inadequate. In order to obtain a branched copolymer having a high content of polypropylene side chains and having excellent reforming performance, the terminal vinyl-type polypropylene macromonomer produced in the pre-polymerization can be dissolved well in the post-polymerization. There is a need for a good copolymerizable catalyst capable of efficiently copolymerizing and polymerizing at high temperature (90 ° C. or higher).

JP 2007-211189 A Unexamined-Japanese-Patent No. 2003-327758 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 the present invention is to provide a propylene-based resin composition which is excellent in the balance between rigidity and impact resistance.

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

[1] 50 to 98 parts by mass of a propylene-based resin (α) and 2 to 50 parts by mass of an olefin-based resin (β) satisfying the following requirements (I) to (VI) other than the propylene-based resin (α) The total of the resin ((alpha)) and the said olefin resin ((beta)) is 100 mass parts, The propylene resin composition characterized by the above-mentioned.
(I) The olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene / α-olefin copolymer and a side chain made of a propylene polymer.
(II) When the proportion 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 peak value of the differential elution curve measured by a cross fractionation chromatograph (CFC) using ortho-dichlorobenzene as a solvent and having a peak value of less than 65 ° C. with respect to the olefin resin (β) When it does, the value a represented by a 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 amount of thermal xylene insoluble 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 proportion of ethylene-derived units contained in the olefin resin (β) is in the range of 20 to 80 mol% with respect to all monomer-derived units contained in the olefin resin (β). Description Propylene-based resin composition.

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

  [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 5000 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 50000 to 200000 of [1] to [4] The propylene resin composition as described in any one.

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

(A) Polymerization of propylene in the presence of a catalyst for olefin polymerization containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilyl bisindenyl skeleton to produce a terminally unsaturated polypropylene Process,
(B) In the presence of a catalyst for olefin polymerization containing a bridged metallocene compound represented by the following formula [B], the terminally unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms A step of copolymerizing with at least one α-olefin selected from the group consisting of α-olefins of

(In 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, a hydrocarbon group, a silicon-containing group or a silicon-containing group The other hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

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

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 hetero atom-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 represent an aryl group.

Y ¹ represents a carbon atom or a silicon atom.

M ¹ represents a zirconium atom or a hafnium atom.

  Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair In the case where j is an integer of 1 to 4 and j is an integer of 2 or more, plural 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 of performing copolymerization at 90 ° C. or higher.

  [8] A molded article 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 which is 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-based resin composition according to the present invention comprises 50 to 98 parts by mass of a propylene-based resin (α) and an olefin-based resin (β) 2 satisfying requirements (I) to (VI) other than the propylene-based resin (α). And 50 parts by mass. In addition, the sum total of the said propylene resin ((alpha)) and the said olefin resin ((beta)) is 100 mass parts.

  The content of the propylene-based resin (α) is preferably 55 to 95 parts by mass, more preferably 60 to 90 parts by mass, still more preferably 65 to 85 parts by mass, and particularly preferably 65 to 80 parts by mass. Moreover, 5-45 mass parts is preferable, 10-40 mass parts is more preferable, 15-35 mass parts is more preferable, and, as for content of olefin resin ((beta)), 20-35 mass parts is especially preferable. When the content ratio of the propylene-based resin (α) and the olefin-based resin (β) is in the above range, impact resistance and toughness are improved while maintaining good properties such as rigidity and hardness inherent to the propylene-based resin. Thus, the propylene-based resin composition can be suitably used for the production of various molded articles.

<Propylene-based 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, 1 Decene, 1-undecene, 1-dodecene, and the like. Among these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

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

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

  The homopolypropylene resin is a resin substantially consisting of a propylene homopolymer, is inexpensive and easy to manufacture, is excellent in rigidity and surface hardness, but is inferior in impact resistance and toughness. 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 resin (β) maintains impact resistance while maintaining the rigidity and the like of the homopolypropylene resin. It is possible to improve the quality and toughness.

  The random polypropylene resin is a resin composed mainly of a propylene polymer containing a small amount of a comonomer, and has high impact resistance and transparency compared to the homopolypropylene resin. In the propylene-based resin composition according to the present invention, when a random polypropylene resin is used as the propylene-based resin (α), impact resistance, toughness, and rigidity are maintained by the olefin-based resin (β) while maintaining the rigidity of the random polypropylene resin. The surface hardness can be improved, in particular the low temperature impact resistance can be improved.

  Block polypropylene resin is a two-stage polymerization composition of propylene polymer and ethylene propylene copolymer, and the term "block" of 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 to 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) can not achieve the block polypropylene resin alone, such as rigidity and impact resistance It is possible to enhance the reciprocal physical properties of the

  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 min, more preferably 0.2 to 300 g / 10 min, 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-based resin (α) is 0.1 g / 10 min or more, the dispersibility of the propylene-based resin (α) and the olefin-based resin (β) in the propylene-based resin composition is improved. The mechanical strength of the composition is improved. In addition, when the MFR of the propylene-based resin (α) is 500 g / 10 min or less, the strength of the propylene-based resin (α) itself is improved, and the mechanical strength of the resin composition is improved. In addition, MFR becomes a parameter | index of the molecular weight of propylene-type resin ((alpha)).

  The weight average molecular weight of propylene-based resin (α) in terms of polypropylene, determined by gel permeation chromatography (GPC), is preferably 80,000 to 900,000, more preferably 100,000 to 700,000, 150,000 to 700,000 More preferable.

  500-3000 Mpa is preferable, as for the tensile elasticity modulus of propylene-type resin ((alpha)), 600-2500 Mpa is more preferable, and 650-2200 Mpa is still more preferable. When the tensile modulus is in the above range, the propylene-based resin composition exhibits high rigidity and high hardness. The tensile modulus of elasticity is a value measured at 23 ° C. using a 2 mm-thick press sheet in accordance with JIS K7113-2.

  The propylene-based resin (α) is different from the propylene polymer contained in the olefin-based resin (β). The terminal structure of the propylene-based resin (α) can be substantially saturated hydrocarbon, and 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 the following requirements (I) to (VI). Further, the olefin resin (β) preferably satisfies at least one of the following requirements (VII) to (IX). In addition, an 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) contains a graft type olefin polymer [R1] having a main chain consisting of an ethylene / α-olefin copolymer and a side chain consisting of a propylene polymer.
(II) When the proportion 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 peak value of the differential elution curve measured by cross fractionation chromatograph (CFC) using orthodichlorobenzene as a solvent at a peak value of less than 65 ° C. to the olefin resin (β) is E mass% At the same time, 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 amount of thermal xylene insoluble 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 proportion of units derived from ethylene contained in the olefin resin (β) is 20 to 80 mol% with respect to units derived from all the 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 ortho-dichlorobenzene soluble component at 50 ° C. or less measured by cross fractionation chromatography (CFC) is 50% by mass or less.

  The details of each requirement will be described below.

(Requirement (I))
The olefin resin (β) includes a graft type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of 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, “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 consisting of a propylene polymer is chemically bonded to a main chain consisting 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 a propylene resin containing an ethylene / α-olefin copolymer having a linear structure. For this reason, the propylene-based resin composition containing the olefin-based resin (β) and the propylene-based resin (α) can exhibit an excellent balance of physical properties.

It is preferable that the main chain and the side chain of the graft type olefin polymer [R1] satisfy the following requirements (i) to (iv).
(I) The main chain is composed of a unit derived from ethylene and a unit derived from at least one α-olefin selected from the group consisting of an α-olefin having 3 to 20 carbon atoms, a unit derived from the α-olefin The ratio of is within the range of 10 to 50 mol% with respect to the units derived from all the monomers contained in the main chain.
(Ii) The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain is 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 which comprises a side chain is 5000-100000.

  The details of each requirement will be described below.

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

  The main chain of the graft type olefin polymer [R1] is composed of an ethylene / α-olefin copolymer, and in the graft type olefin polymer [R1], flexibility, low temperature properties required as a modifier, etc. It is a part responsible for the characteristic. In order to ensure such properties, 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 a unit derived from α-olefin.

  Specific examples of the C3-C20 α-olefin 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-ene Butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1 -Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1 Nonene, 1-decene, 1-undecene, 1-dodecene, and the like.

  The C3 to C20 alpha-olefin is preferably a C3 to C10 alpha-olefin, and more preferably a C3 to C8 alpha-olefin. 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, and propylene, 1-butene, 1-pentene, 1-hexene, 1-octene are more preferred, 1-butene, 1-pentene, 1-hexene, 1-octene Octene is more preferred. In particular, by using 1-butene, 1-pentene, 1-hexene, or 1-octene as the C3-C20 α-olefin, a propylene-based material having particularly good balance of physical properties between rigidity and impact resistance A resin composition is obtained.

  The proportion of units derived from ethylene in the main chain of the graft type olefin polymer [R1] is preferably 50 to 90 mol%, and 60 to 90 mol% with respect to the units derived from all the monomers contained in the main chain. It is more preferable that In addition, the proportion of units derived from at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms is 10 to 50 mol% with respect to units derived from all the monomers contained in the main chain Is preferably, and more preferably 10 to 40 mol%. Although the relationship between the proportion of units derived from ethylene and an α-olefin and the glass transition temperature (Tg) differs depending on the type of α-olefin used, the range of the glass transition temperature (Tg) of the requirement (IV) is achieved 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. In addition, when the proportion of units derived from ethylene and α-olefin in the main chain is in the above range, the olefin resin (β) has high flexibility and excellent low temperature properties, 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 obtained olefin resin (β) becomes a resin inferior in flexibility and low temperature characteristics, and a propylene resin composition containing the resin is inferior in low temperature impact resistance There is a case.

  The molar ratio of units derived from ethylene and α-olefin in the main chain is controlled by controlling the ratio of the concentration of ethylene to the concentration of α-olefin in the polymerization reaction system in the step of producing the main chain. It can be adjusted. In addition, the molar ratio of units derived from α-olefin contained in the main chain is, for example, the α-olefin composition of ethylene / α-olefin copolymer obtained under the condition not containing terminal unsaturated polypropylene described later. And the influence of terminally unsaturated polypropylene and side chains from the α-olefin composition of the olefin resin (β).

(Requirement (ii))
The weight-average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft type olefin polymer [R1] is preferably in the range of 50000 to 200000. In the propylene-based resin composition according to the present invention, the weight average molecular weight is more preferably in the range of 10000 to 200000 from the viewpoint of improving the moldability (flowability) of the resin while maintaining the mechanical strength, and 120,000 More preferably, it is in the range of -180,000.

  When the weight average molecular weight is in the above range, the propylene resin composition containing an olefin resin (β) tends to have a better balance of impact resistance, rigidity and toughness. On the other hand, when the weight average molecular weight is less than 50,000, impact resistance and toughness may be reduced. When the weight average molecular weight exceeds 200,000, poor dispersion in a propylene-based resin may occur, making it difficult to obtain a desired balance of physical properties.

  The said weight average molecular weight can be adjusted by controlling the ethylene concentration in a polymerization system in the manufacturing process mentioned later. As a control method of ethylene concentration, adjustment of ethylene partial pressure adjustment and adjustment of polymerization temperature are mentioned. The adjustment of the weight average molecular weight is also possible 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 may be determined, for example, by analyzing an ethylene / α-olefin copolymer when it is produced under the condition not containing terminal unsaturated polypropylene described later, or by analyzing an olefin resin (β). It is determined from the subtraction of effects derived from polypropylene and side chains.

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

  The propylene polymer substantially consisting of units derived from propylene means propylene having a molar ratio of units derived from propylene of 99.5 to 100 mol% with respect to units derived from all the monomers contained in the propylene polymer. It is possible to show coalescence. That is, a small amount of α-olefin other than propylene may be copolymerized as long as the role and characteristics are not impaired.

  In particular, the isotactic pentad fraction (mm mm) of the propylene polymer constituting the side chain of the graft type olefin polymer [R1] is preferably 93% or more, and is 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 a high melting point isotactic polypropylene polymer, the compatibility of the olefin resin (β) with the propylene resin is improved. For this reason, the resulting propylene-based resin composition can maintain good rigidity and hardness while exhibiting good impact resistance.

  The graft type olefin polymer [R1] is, for example, copolymerized with terminal unsaturated polypropylene produced in the step (A), and ethylene and an α-olefin in the production step (B) of the olefin resin (β) described later. It can be obtained by That is, the composition and stereoregularity of the terminally unsaturated polypropylene correspond to the composition and stereoregularity of the side chain of the grafted olefin polymer [R1]. Therefore, the composition and stereoregularity of the terminally unsaturated polypropylene produced in the step (A) are calculated using a known method, and the composition and stereoregularity are the composition of the side chain of the grafted olefin polymer [R1]. And can be defined as stereoregularity. Specifically, mm mm is a value measured by the method described later.

(Requirement (iv))
It is preferable that the weight average molecular weights of the propylene polymer which comprises the side chain of graft type olefin polymer [R1] exist in the range of 5000-100000. 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, and a propylene polymer It is preferred that the site be a side chain. The weight average molecular weight is more preferably 5,000 to 60,000, and still more preferably 5,000 to 25,000.

  When the weight average molecular weight is in the above range, the compatibility between the propylene resin (α) and the olefin resin (β) is enhanced, and propylene containing the propylene resin (α) and the olefin resin (β) The impact resistance and elongation at break of the resin composition are well developed, and the flowability in injection molding is also improved. On the other hand, when the weight average molecular weight is less than 5,000, the interfacial strength with the propylene-based resin (α) may be weakened, and the elongation and impact resistance of the propylene-based resin composition may be reduced. Moreover, when the said weight average molecular weight exceeds 100,000, the fluidity | liquidity at the time of shaping | molding of an olefin resin ((beta)) may become low, and processability may fall. In addition, the compatibility between the propylene-based resin (α) and the olefin-based resin (β) decreases, and the tensile elongation and the resistance of the propylene-based resin composition containing the propylene-based resin (α) and the olefin-based resin (β) The impact resistance may be reduced, or the surface hardness of the molded product obtained from the propylene-based resin composition may be reduced.

  Examples of the method of adjusting the weight average molecular weight include a method of adjusting the polymerization temperature and the polymerization pressure in the production process (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 by process (A) by a conventional method similarly to said requirement (iii). For example, the weight-average molecular weight in terms of polypropylene of the terminally 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 proportion (hereinafter, also referred to as a proportion 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) means, for example, a polypropylene side chain taken into the main chain in the step (B) described later and a polypropylene linear polymer not taken into the main chain. Indicates the sum of The proportion P is more than 20% by mass, preferably 50% by mass or less, more than 20% by mass, more preferably 40% by mass or less, and still more 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-based resin (α) and the olefin-based resin (β) is enhanced, and a propylene-based resin containing the propylene-based resin (α) and the olefin-based resin (β) The impact resistance of the composition is well developed. 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 obtained propylene-based resin composition does not exhibit good physical properties in impact resistance. Moreover, when the ratio P exceeds 60 mass%, relative content of ethylene-alpha-olefin copolymer decreases, and the obtained propylene-type resin composition does not express a favorable physical property in low-temperature impact resistance.

  The ratio P is determined, for example, from the ratio of the mass of the terminally unsaturated polypropylene used in the step (B) described later and the mass of the obtained olefin resin (β).

  In addition, terminally unsaturated polypropylene means the polypropylene which has the terminal unsaturation represented by the following terminal structure (I)-(IV). "Poly" in terminal structure (I)-(IV) shows the coupling | bonding position of terminal structure and propylene polymer molecular chains other than this terminal structure.

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

In addition, quantification of the said terminal unsaturation can be performed by determining the terminal structure of a terminally unsaturated polypropylene by ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The assignment of the terminal structure can be performed according to the method described in Macromolecular Rapid Communications 2000, 1103 or the like.

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

(Requirement (III))
In the olefin resin (β), the ratio of the component having a peak temperature of the differential elution curve measured by cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent to a peak temperature of less than 65 ° C. to the olefin resin (β) Hereinafter, when the proportion E is E mass%, a value a (hereinafter also referred to as an 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, more preferably 2.2 or more.

The differential elution curve is obtained by differentiating the accumulated elution curve obtained at an elution temperature in the range of -20 ° C to 140 ° C. Furthermore, the component ratio of each elution peak can be determined by separating each elution peak appearing in the differential elution curve into a normal distribution curve. Here, E _{(<−20 ° C.)} mass, where the fraction of soluble components at less than −20 ° C. (proportion of the component not coated in the temperature rising elution fractionation (TREF) column even at −20 ° C. in the cooling step of CFC measurement ₎ %, - 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%, the proportion of components which do not dissolve at 140 ° C. is E _{(> 140 ° C.)} mass%, E _{(<-20 ° C.)} + E _{(<65 ° C.)} + E _{(≧ 65 ° C.)} + E _{(> 140 ° C.)} = 100 When mass% is used, it is defined as a ratio E = E _{(<−20 ° C.)} + E _{(<65 ° C.)} . In general, olefin resin (β) is totally soluble in ortho-dichlorobenzene at 140 ° C., and it is possible to detect a clear peak whose peak separation is easy at 65 ° C. or higher, E _{(> 140 ° C.)} = In the case of 0, it is defined as the ratio E = 100−E _{(≧ 65 ° C.)} .

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

  The proportion E and the proportion P are proportions 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 resin, additive, etc. Not included in

  The fact that the a value is within the above range means that the olefin resin (β) corresponds to the graft type olefin polymer [R1], that is, an ethylene / α-olefin copolymer having a propylene polymer moiety as a side chain. Indicates that 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 indicating the relationship of a = 1.0 indicates the case where the graft type olefin polymer [R1] is not contained, that is, the case of a mixture of ethylene / α-olefin copolymer and propylene polymer. . On the other hand, as the a value increases and the content of the graft-type olefin polymer [R1] increases, the value of the ratio E to the ratio P decreases. A large value for the a value indicates that the content of the graft type olefin polymer [R1] is high. The olefin resin (β) according to the present invention is characterized in that the a value is 1.4 or more.

  In general, a commercially available olefin-based elastomer used for polypropylene resin modifiers and the like comprises ethylene / α-olefin copolymer (eg, ethylene / butene copolymer or ethylene / octene copolymer), and has a composition of ethylene Is a polymer adjusted to about 90 mol% to 50 mol%. Therefore, the proportion E of the eluted components of the conventional 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 to play a role of imparting improvement in impact resistance. When the blending amount of the olefin elastomer is increased, the impact resistance is improved, but the inherent rigidity and mechanical strength of the propylene resin are reduced. For this reason, generally, in a polypropylene resin composition, impact strength and rigidity become reciprocal physical properties.

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

  When such an olefin resin (β) is blended in a propylene resin (α), the polypropylene side chain of the graft type olefin polymer [R1] has a good affinity with the propylene resin (α), so the result is Specifically, it has a feature of forming a phase separation structure in which an ethylene / α-olefin copolymer is finely dispersed in a propylene-based 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 in an incompatible relationship with each other. It is thought that it enters the crystal of (α) and exhibits the effect of enhancing the strength of the interface. Therefore, a propylene-based composition containing an olefin-based resin (β) containing a large amount of a graft-type olefin-based polymer [R1] is excellent in impact resistance, high in rigidity and mechanical strength, and excellent in elongation. The surface hardness of the resulting molded article also increases, resulting in a composition having an improved balance of physical properties.

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

  130-160 degreeC is preferable and, as for melting | fusing point (Tm), 140 degreeC-160 degreeC is more preferable. 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 ° C. to 160 ° C.

  The temperature at which the melting peak appears, that is, the melting point (Tm) and the heat of melting (ΔH) described later are caused to melt the sample by DSC once after being heated by DSC and then crystallized by cooling to 30 ° C. The endothermic peak appearing in the temperature raising step (temperature raising rate of 10 ° C./min) is analyzed.

  The melting point (Tm) and the heat of fusion (ΔH) observed in the above range mainly originate from the polypropylene side chain of the graft type olefin polymer [R1] constituting the olefin resin (β). The olefin resin (β) is well compatible with the propylene resin (α) when the melting point (Tm) is in the above range, and more preferably the heat of fusion (ΔH) is in the range described later 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. As a method of adjusting melting | fusing point (Tm) in the said range, the method of adjusting polymerization temperature and polymerization pressure is mentioned in the manufacturing process (A) mentioned later.

  -80.0--40.0 degreeC is preferable, -80.0--50.0 degreeC is more preferable, and -80.0--60.0 degreeC is further more preferable for glass transition temperature (Tg). The glass transition temperature (Tg) mainly originates from the nature of the ethylene / α-olefin copolymer of the main chain of the graft type olefin polymer [R1]. When the glass transition temperature (Tg) is in the range of -80.0 ° C to -30.0 ° C, the propylene-based resin composition containing the olefin-based resin (β) exhibits a good 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 a thermal xylene insoluble content 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 It is further preferred that The amount of insoluble thermal xylene may be 0% by mass. The olefin-based resin (β) can be well dispersed in the propylene-based resin (α) because the amount of insoluble in thermal xylene is 3% by mass or less, and as a result, the desired effect is exhibited. On the other hand, when the amount of the thermal xylene insoluble portion exceeds 3% by mass, an appearance defect called "butsu" occurs in a molded product obtained from the propylene 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 heat pressing (180 ° C., heating for 5 minutes, cooling for 1 minute), and cut into pieces. It is weighed about 100 mg, wrapped in a 325 mesh screen and immersed in 30 ml of p-xylene in a closed container at 140 ° C. for 3 hours. The screen is then removed and dried at 80 ° C. for 2 hours more until constant weight. 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: The total mass of the screen and sample before the test, W2: The mass of the screen, W3: The total mass of the screen and the sample after the test.

  The thermal xylene insoluble amount can be adjusted within the above range by adopting a method of directly obtaining a graft-type olefin polymer 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 in 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 MFR Since it can be enhanced, it also has good moldability. The intrinsic viscosity [粘度] 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 the monomers contained in the olefin resin (β) %, More preferably 40 to 80 mol%, particularly preferably 40 to 75 mol%. When the ratio is in the above range, the olefin resin (β) becomes an embodiment containing more ethylene / α-olefin copolymer, and the propylene resin composition containing the olefin resin (β) has an impact resistance Sex is good.

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

  The melting peak is derived from the side chain consisting 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 fact that the heat quantity (ΔH) is within the above range indicates that a considerable amount of side chain sites of the graft type olefin polymer [R1] contained in the olefin resin (β) is contained. In the olefin resin (β) according to the present invention, due to the presence of the polypropylene side chain of the graft type olefin polymer [R1], the stickiness is small and physical properties like a heat resistant elastomer can be expressed.

  On the other hand, when the heat of fusion (ΔH) is less than 5 J / g, the proportion of the polypropylene side chains is small, so there may be no heat resistance and high stickiness, as with linear olefin elastomers. In addition, the reforming effect in the propylene-based resin as described above may not be sufficient. When the heat of fusion (ΔH) exceeds 50 J / g, properties derived from the ethylene / α-olefin copolymer such as flexibility and low temperature properties 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 a component soluble in ortho-dichlorobenzene at 50 ° C. or less measured by cross fractionation chromatography (CFC) is preferably 50% by mass or less, and 40% by mass or less Is more preferred.

  By satisfying the requirement (IX) in addition to the requirement (III), the effect of including the graft type olefin polymer [R1] becomes higher, and the stickiness of the olefin resin (β) becomes lower, and the handling Sex is good. Furthermore, even in the case of a propylene-based composition containing an olefin-based resin (β), the impact resistance is excellent, the rigidity and mechanical strength are high, the elongation is also excellent, and the surface hardness of the obtained molded article is also high. It is inferred that the composition is a further improved composition.

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

  The olefin resin (β) is preferably further free of substances that cause coloration, offensive odor, and contamination of the final product. Specific examples of the substance causing the coloration, the offensive odor and the contamination of the final product include hetero atom-containing compounds. Examples of the hetero atom-containing compound include compounds containing halogen atoms such as chlorine atoms and bromine atoms, compounds containing chalcogen atoms such as oxygen atoms and sulfur atoms, compounds containing pnictogens such as nitrogen atoms and phosphorus atoms, etc. Be Specifically as a compound containing the said oxygen atom, a maleic anhydride and a maleic anhydride reactant are mentioned. Moreover, metal atom-containing compounds may also be mentioned as substances causing coloration, offensive odor and contamination of final products, and more specifically, alkali metal-containing compounds such as sodium and potassium, alkaline earths such as magnesium and calcium Metal-containing compounds are mentioned.

  1000 mass ppm or less is preferable, as for content of the said hetero atom containing compound of olefin resin ((beta)), 100 mass ppm or less is more preferable, and 10 mass ppm or less is more preferable. Moreover, 1000 mass ppm or less is preferable, as for content of the said metal atom containing compound of 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, rubber, inorganic fillers such as talc, organic fillers, and the like within the range that does not impair the object of the present invention. In addition, the propylene-based resin composition according to the present invention is a weather resistant stabilizer, a heat resistant stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, an antiaging agent And additives such as hydrochloric acid absorbents, antioxidants and nucleating agents. The content of the other resin, rubber, inorganic filler, organic filler, additive and the like is not particularly limited as long as the object of the present invention is not impaired.

[Method for producing 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 step (A) and step (B).

(A) Polymerization of propylene in the presence of a catalyst for olefin polymerization containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilyl bisindenyl skeleton to produce a terminally unsaturated polypropylene Process,
(B) In the presence of a catalyst for olefin polymerization containing a bridged metallocene compound represented by the following formula [B], the terminally unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms A step of copolymerizing with at least one α-olefin selected from the group consisting of α-olefins of

(In 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, a hydrocarbon group, a silicon-containing group or a silicon-containing group And R ^{2 to} R ⁴ may be bonded to each other to form a ring, R ⁶ and R ^{11 each} represents a hydrogen atom or a hydrocarbon. R ⁷ and R ^{10 each} represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, and the like, which are selected from the group consisting of a silicon-containing group and a hetero atom-containing group other than a silicon-containing group. R ⁶ and R ⁷ may be bonded to each other to form a ring, R ¹⁰ and R ¹¹ may be the same atom or the same group selected from the group consisting of heteroatom-containing groups other than silicon-containing groups; Are joined together to form a ring However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms, and R ¹³ and R ¹⁴ each independently represent an aryl group Y ¹ is a carbon atom or a silicon atom M ¹ represents a zirconium atom or a hafnium atom, Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or A neutral ligand capable of coordinating with a lone electron pair is shown, j is an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Q may be the same or different.) .

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

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

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

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

  Examples of the transition metal compound [A] contained in the olefin polymerization catalyst used to produce such a highly stereoregular and highly terminally unsaturated polypropylene having a terminal structure (I) are, for example, JP-Hei 6-100579, JP-A-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443, etc. Compounds are mentioned.

  More specifically, the transition metal compound [A] is dimethylsilyl bis (indenyl) zirconocene or hafnocene. More preferably, it is dimethylsilyl bis (indenyl) zirconocene. By selecting zirconocene, the formation of a long chain branched polymer caused by the insertion reaction of the terminal unsaturated polypropylene is suppressed, and the propylene-based resin composition containing the olefin-based resin (β) expresses desired physical properties. On the other hand, when a large amount of the long chain branched polymer is produced in the step (A), the propylene resin composition containing the olefin resin (β) may deteriorate 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. One of these may be used, or two or more may be used in combination.

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

  50 degreeC-200 degreeC are preferable, 80 degreeC-150 degreeC are more preferable, and, as for the superposition | polymerization temperature of a process (A), 80 degreeC-130 degreeC are more preferable. By controlling the polymerization temperature within the above range, a terminally 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, and more preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out either batchwise, semicontinuously or continuously. In the present invention, among these, the method of continuously supplying monomers to the reactor to carry out copolymerization is preferable.

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

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

  The weight average molecular weight of the terminally unsaturated polypropylene produced in the step (A) is preferably in the range of 5000 to 100000, more preferably in the range of 5000 to 60000, and in the range of 5000 to 25000. It is further preferred that When the weight average molecular weight is within the above range, the molar concentration of the terminally unsaturated polypropylene can be increased relative to ethylene or α-olefin in the step (B) described later, and the introduction into the main chain Efficiency is high. On the other hand, when the weight average molecular weight exceeds 100,000, the molar concentration of the terminally unsaturated polypropylene may be relatively low, and the introduction efficiency to the main chain may be low. When the weight average molecular weight is less than 5,000, the melting point may be lowered.

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

The proportion of terminal unsaturation as measured by ¹ H-NMR of the terminally unsaturated polypropylene produced in step (A) is preferably 0.1 to 10.0 per 1000 carbon atoms, More preferably, it is 4 to 5.0. Furthermore, the proportion of terminal unsaturation having the terminal structure (I), the so-called terminal vinyl content, is preferably 0.1 to 2.0 per 1000 carbon atoms, and 0.4 to 2.0 It is more preferable that When the amount of terminal vinyl is small, the amount of terminal unsaturated polypropylene introduced into the main chain in the subsequent step (B) is small, and the amount of graft-type olefin polymer [R1] is small. There are cases where the effect can not be obtained. The calculation of the amount of terminal unsaturation and the ratio of each terminal structure by ¹ H-NMR measurement can be performed, for example, according to the method described in Macromolecular Rapid Communications 2000, 1103.

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

  In the step (B), it is important to select a highly copolymerizable and high molecular weight catalyst which expresses sufficient activity at high temperature. The terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and has a sterically bulky structure, so polymerization is more difficult than linear vinyl monomers. In addition, terminal vinyl polypropylene is less likely to be copolymerized under low temperature conditions in which the polymer precipitates. For this reason, the catalyst is preferably required to exhibit sufficient activity at a polymerization temperature of 90 ° C. or higher, and have a performance capable of achieving a desired molecular weight of the main chain. 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 terminally unsaturated polypropylene produced in step (A), ethylene and an α-olefin having 3 to 20 carbon atoms, together with compound [C] described later It functions as a catalyst for olefin polymerization which copolymerizes with at least one α-olefin.

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

  The bridged metallocene compound [B] has the following features [m1] and [m2] in structure.

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

  [M2] The two ligands are linked by an aryl group-containing covalent bond bridge (hereinafter also referred to as "bridge") consisting of a carbon atom having an aryl (aryl) group or a silicon atom.

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

(Cyclopentadienyl group which may have a substituent)
In the formula [B], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group. From the viewpoint of better incorporation of terminal vinylpolypyrene, all of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, or at ^{least one} of R ¹ , R ² , R ³ and R ⁴ is 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 hetero atom-containing group other than a silicon-containing group, and a hydrogen atom, Hydrocarbon 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 hetero atom-containing group other than a silicon-containing group, a hydrogen atom, a hydrocarbon group and Preferred are the same atoms or the same groups selected from the group consisting of silicon containing groups. 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 hetero atom-containing group other than a silicon-containing group, a hydrogen atom, a hydrocarbon group and Preferred are the same atoms or the same groups selected from the group consisting of silicon containing groups. 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 is preferably not ^{R 6} and ^{R 11} each is hydrogen ^atom, R ^6, R ^{7, R 10} and ^{R 11} are more preferably not both hydrogen atoms, ^{R 6} and ^{R 11} is It is further preferred that R ⁷ and R ¹⁰ 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 bond together to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ bond together to form an alicyclic or aromatic ring.

The hydrocarbon group in R ⁵ ~R ^12, (sometimes referred to as the "hydrocarbon group (f1)") hydrocarbon group having 1 to 20 carbon atoms can be mentioned. Moreover, as a silicon-containing group in R < ⁵ > -R < ¹² >, a C1-C20 silicon-containing group (Hereafter, it may refer as a "silicon-containing group (f2).") Is mentioned. Examples of the hetero atom-containing group other than the silicon-containing group in R ^{5 to} R ¹² include hetero atom-containing groups such as halogenated hydrocarbon group, oxygen-containing group, nitrogen-containing group (excluding silicon-containing group (f2)). .

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

  Among the hydrocarbon group (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 groups in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group, and specific examples thereof include an alkylsilyl group (eg, trimethylsilyl group), an aryl And silyl groups (eg, triphenylsilyl group).

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

As a substituted fluorenyl group when R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) combine with each other to form an alicyclic or aromatic ring, they are derived from the compounds represented by formulas [II] to [VI] described later Preferred groups.

(Crosslinked part)
In formula [B], R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. The important point in the production of the olefin polymer is that the crosslinking atom Y ¹ in the crosslinking portion has R ¹³ and R ¹⁴ which are aryl groups which may be the same or different from each other. R ¹³ and R ¹⁴ are preferably identical to each other for ease of production.

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

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

(Other features of bridged metallocene compound [B])
In the above Formula [B], Q can be coordinated with a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a lone electron pair A neutral ligand is shown, j is 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.

  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. As an aliphatic hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3 -A trimethylbutyl group and neopentyl group are mentioned. As an alicyclic hydrocarbon group, a cyclohexyl group, a cyclohexylmethyl group, 1-methyl- 1-cyclohexyl group is mentioned, for example.

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

In Formula [B], M ¹ represents a zirconium atom or a hafnium atom. It is preferable that M ^{1 be} a hafnium atom from the viewpoint of highly efficiently copolymerizing terminally unsaturated polypropylene and controlling its molecular weight to high. It is important to ensure high productivity that a terminally unsaturated polypropylene be copolymerized with high efficiency and a catalyst with performance that can be controlled to high molecular weight is used. This is because it is desirable to carry out the reaction under high temperature conditions in order to ensure high productivity, but there is a tendency for a decrease in molecular weight to occur under high temperature conditions.

(Exemplification of preferred bridged metallocene compound [B])
Below, the specific example of bridge | crosslinking metallocene compound [B] is shown. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl represents a group derived from a compound having a structure represented by the following formula [II]. Octamethyltetrahydrodicyclopentafluorenyl represents a group derived from a compound having a structure represented by the following formula [III]. Dibenzofluorenyl indicates 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 represents 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 represents a group derived from a compound having a structure represented by the following formula [VI].

  Although di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride is used as such a bridged metallocene compound [B] in the examples described later, the present invention The bridged metallocene compound [B] according to the present invention is not limited to this compound, and all bridged metallocene compounds exemplified in WO 2005/100410 can be used without limitation.

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

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

  Step (B) can be carried out in solution (dissolution) polymerization. In particular, it is preferable that the step (B) be a solution polymerization step in which copolymerization is performed at 90 ° C. or higher. The polymerization method is not particularly limited as long as a solution polymerization step for producing an olefin-based polymer is used, but it is preferable to have a step of obtaining the following polymerization reaction solution.

In the step of obtaining a polymerization reaction solution, an aliphatic hydrocarbon is used as a polymerization solvent, and a crosslinked metallocene compound [B], preferably R ¹³ and R ¹⁴ bonded to Y ¹ in the above formula [B] is a phenyl group Or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a metallocene catalyst comprising a compound substituted with an alkyl group or a halogen group, wherein R ⁷ and R ¹⁰ represent an alkyl substituent. And a step of obtaining a polymerization reaction solution of a copolymer with the terminally unsaturated polypropylene produced in the step (A).

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

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

  90 degreeC-200 degreeC are preferable, and, as for the superposition | polymerization temperature of a process (B), 100 degreeC-200 degreeC are more preferable. The temperature at which the terminally unsaturated polypropylene dissolves well in an aliphatic hydrocarbon such as hexane or heptane preferably used industrially as the polymerization solvent is 90 ° C. or higher, so that the polymerization temperature is 90 ° C. or higher Is preferred. In addition, it is preferable that the polymerization temperature be higher from the viewpoint of the improvement of the introduction amount of polypropylene side chains and the improvement of productivity.

  The polymerization pressure in the step (B) is preferably normal pressure to 10 MPa gauge pressure, and more preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out either batchwise, semicontinuously or continuously. Furthermore, it is also possible to divide the polymerization into two or more stages under different reaction conditions. In the present invention, among these, the method of continuously supplying monomers to the reactor to carry out copolymerization is preferable.

  The reaction time of the step (B) (average residence time when the copolymerization is carried out continuously) varies depending on conditions such as catalyst concentration, polymerization temperature, etc., preferably 0.5 minutes to 5 hours, 5 Minutes to 3 hours are more preferred.

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

  The molecular weight of the resulting copolymer can also be controlled by the presence of hydrogen in the polymerization system or by varying the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound [C1] described later. Specific examples of the compound [C1] include triisobutylaluminum, methylaluminoxane, diethyl zinc and the like. When hydrogen is added, the amount of hydrogenation is preferably 0.001 to 100 NL per kg of olefin.

<Compound [C]>
In the step (A) and the step (B), the compound [C] is preferably used together with the transition metal compound [A] and the crosslinked metallocene compound [B] used as a catalyst for olefin polymerization.

  The compound [C] reacts with the transition metal compound [A] and the bridged metallocene compound [B] to function as a catalyst for olefin polymerization. As the compound [C], specifically, [C1] organic metal compound, [C2] organoaluminum oxy compound, and [C3] transition metal compound [A] or crosslinked metallocene compound [B] react with ions The compound which forms a pair is mentioned. The compounds of [C1] to [C3] will be sequentially described below.

([C1] Organometallic Compound)
[C1] As the organometallic compound, specifically, an organoaluminum compound represented by the following formula (C1-a), a complex of a periodic table group 1 metal represented by the following formula (C1-b) and aluminum Examples thereof include alkyl compounds and dialkyl compounds of metals of Groups 2 or 12 of the periodic table represented by the following Formula (C1-c). Note that the [C1] organic metal 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)
M < ³ > shows Li, Na, or K in said Formula (C1-b). 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.

  As an organic aluminum compound represented by said Formula (C1-a), the compound represented by following formula (C-1a-1)-(C-1a-4) can be illustrated.

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), R ^a 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, tri-sec-butylaluminum, tri-tert-butylaluminum and the like;
Tricycloalkyl aluminum such as tricyclohexyl aluminum;
Triarylaluminum such as triphenylaluminum, tritolylaluminum etc.
Dialkyl aluminum hydride such as diisobutyl aluminum hydride;
(IC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein, x, y, z are positive numbers, and z ≧ 2x) Of trialkenyl aluminum;
Alkyl aluminum alkoxide of isobutyl aluminum methoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;
Partially alkoxylated alkyl aluminum having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 , wherein R ^a and R ^b are each independently 1 to 15 carbon atoms Preferably a hydrocarbon group having 1 to 4 carbon atoms);
Dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride and dibutylaluminum chloride;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride;
Partially alkoxylated and halogenated alkyl aluminum and the like such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxy bromide can be mentioned.

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

The compound represented by the formula (C1-b), and the like _{LiAl (C 2 H 5) 4} , LiAl (C 7 H 15) 4.

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

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

  In addition, a compound by which the organoaluminum compound is formed in a polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, etc. is used as the above-mentioned [C1] organic metal 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 may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A No. 2-78687. Specific examples of the organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

The known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension in the above to cause adsorbed water or crystal water to react with the organoaluminum compound.
(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide 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 organic metal component. After distilling off the solvent or unreacted organoaluminum compound from the solution of the aluminoxane recovered, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  As an organic aluminum compound used when preparing the said aluminoxane, the organic aluminum compound similar to what was illustrated as an organic aluminum compound represented by said Formula (C1-a) can be mentioned specifically ,. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is more preferable. These organoaluminum compounds can be used singly or in combination of two or more.

  Examples of 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, and cyclo Alicyclic hydrocarbons such as pentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and gas oil or the aromatic hydrocarbons, the aliphatic hydrocarbons and the halides of the alicyclic hydrocarbons In particular, hydrocarbon solvents such as chlorides and bromides may be mentioned. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Among 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 organic aluminum oxy compound, the Al component dissolved in benzene at 60 ° C. is preferably 10% or less, more preferably 5% or less, and 2% or less in terms of Al atom. More preferable. That is, the benzene-insoluble organoaluminum oxy compound is preferably insoluble or poorly soluble in benzene.

  [C2] The organoaluminum oxy compound can also 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 above-mentioned formula (III) is, for example, an alkylboronic acid represented by the following formula (IV) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁹ -B (OH) ₂ (IV)
In said Formula (IV), R ¹⁹ is synonymous with R ¹⁷ in said Formula (III).

  Specific examples of the alkylboronic acid represented by the formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexyl Boronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic 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 such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the formula (C1-a). As the organic aluminum 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 aforementioned [C2] organoaluminum oxy compounds can be used alone or in combination of two or more.

(A compound which reacts with [C3] transition metal compound [A] or bridged metallocene compound [B] to form an ion pair)
Examples of compounds that form an ion pair by reacting with the [C3] transition metal compound [A] or the bridged metallocene compound [B] (hereinafter referred to as "[C3] ionizing ionic compound") include JP-A 1-501950. Patent Publication Nos. Hei 1 502036, Hei 3 179 005, Hei 3 179 006, Hei 3 207 703, Hei 3 207 704, U.S. Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in the above. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

As said Lewis acid, the compound shown by BR < ₃ > (R is a phenyl group which may have substituents, such as a fluorine, a methyl group, a trifluoromethyl group, or a fluorine) is mentioned. Specifically, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron Etc.

  As said ionic compound, the compound represented, for example by following formula (V) is mentioned.

In the above formula (V), R ²⁰ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptitrilienyl 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 triphenyl carbonium cation, tri (methyl phenyl) carbonium cation, and tri (dimethyl phenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation and the like; N, N-dimethylanilinium cation, N, N-diethylanilinium And N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

  Specific examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation and tri (methyl phenyl) phosphonium cation.

As R ²⁰ , a carbonium cation or an ammonium cation is preferable, and a triphenyl carbonium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are more preferable.

  Moreover, a trialkyl substituted ammonium salt, a N, N-dialkyl anilinium salt, a dialkyl ammonium salt, a triaryl phosphonium salt etc. can also be mentioned as said ionic compound.

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

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

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

  Furthermore, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbe There may also be mentioned sodium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds 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 which is an example of the ionizing ionic compound include decaborane; anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri (n-butyl) ammonium] decaborate Salts; salts of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III) and the like can be mentioned.

  [C3] Specific examples of carborane compounds which are one example of the ionizing ionic compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane and the like, and International Publication WO 2015/100410. The compounds disclosed in the above can be used without limitation.

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

  [C3] An isopoly compound which is an example of an ionizing ionic compound is a compound composed of metal ions of at least one atom selected from the group consisting of vanadium, niobium, molybdenum and tungsten, and is in the molecular form of a metal oxide It can be considered to be an ion species. Specific examples of isopoly compounds include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Further, as the salt, for example, a metal of the group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like of the acid And salts thereof and organic salts such as triphenylethyl salt.

  The aforementioned [C3] ionizing ionic compounds can be used singly or in combination of two or more.

  The [C1] organic metal compound is a process (B) in which the molar ratio (C1 / M) of the [C1] organic metal compound to the transition metal atom (M) in the transition metal compound [A] in the step (A) is In the bridged metallocene compound [B], the molar ratio (C1 / M) to the transition metal atom (M) is preferably 0.01 to 100,000, more preferably 0.05 to 50,000. be able to.

  The [C2] organoaluminum oxy compound is a molar ratio (C2 / M) of the aluminum atom in the [C2] organoaluminum oxy compound to the transition metal atom (M) in the transition metal compound [A] in the step (A). In the bridged metallocene compound [B] in step (B), preferably in an amount such that the molar ratio (C2 / M) to the transition metal atom (M) is 10 to 500,000, more preferably 20 to 100,000. It can be used.

  [C3] The ionizing ionic compound is a process wherein the molar ratio (C3 / M) of the [C3] ionizing ionic compound to the transition metal atom (M) in the transition metal compound [A] in the step (A) is a process 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, in addition to the transition metal compound [A] and the bridged metallocene compound [B], when used in combination with a [C2] organoaluminum oxy compound such as methylaluminoxane as a co-catalyst component, it shows high polymerization activity to the olefin compound.

<Step (C)>
In the present invention, in addition to the step (A) and the step (B) in the production of the olefin resin (β), a step (C) of recovering the polymer produced in the step (B) as required May be implemented. This step is a step of separating the organic solvent used in the step (A) and the step (B) to take out the polymer and converting it into a product form, and existing polyolefins such as solvent concentration, extrusion degassing, pelletizing etc. There is no particular limitation in the process of manufacturing the resin.

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

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

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

  Containers for food use and medical use, for example, dishes, retort containers, frozen storage containers, retort pouches, microwave heat resistant containers, frozen food containers, frozen food containers, food containers such as frozen dessert cups, cups, beverage bottles, retort containers, bottles Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, medicine containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. .

  Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials, freshness Holding film, pharmaceutical packaging material, cell culture bag, cell inspection film, bulb packaging material, seed packaging material, film for vegetable and mushroom cultivation, heat-resistant vacuum formed container, sugar container, lid for sugar beet, commercial wrap film, household use Wrap film, baking carton, etc. may be mentioned.

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

  Other applications include, for example, casings of household electric appliances, hoses, tubes, wire coating materials, insulators for high-voltage wires, tubes for cosmetics and perfume sprays, tubes for medical use, infusion tubes, pipes, wire harnesses, motorcycles and railways. Vehicle / aircraft / ship interior materials, instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, arm box, armrest, airbag case lid, shift knob, assist grip, side step Mats, reclining covers, seats in trunks, seat belt buckles, molding materials such as inner and outer moldings, roof moldings, belt moldings, door seals, automotive sealing materials such as body seals, glass run channels, mudguards, Automotive interior / exterior materials such as cooking plates, step mats, license plate housings, automotive hose members, air duct hoses, air duct covers, air intake pipes, air dam pipes, timing belt cover seals, bonnet cushions, door cushions, damping tires, Special tires such as static tire, car race tire, radio control tire, packing, car dust cover, lamp seal, car boot material, rack and pinion boot, timing belt, wire harness, grommet, emblem, air filter packing, furniture, Footwear, clothing, bags, building materials, skin materials, sealing materials for buildings, waterproof sheets, building materials, gaskets, window films for building materials, window films for core materials, iron core protection members, gaskets, doors, door frames, window frames, rims Floorboards, opening frames, etc. Flooring materials, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, anti-fall films / mats / sheets), health appliance parts, shock absorbing pads, protectors / protective equipment (eg: Helmets, guards), sporting goods (eg sport grips, protectors), sports equipment, rackets, mouth guards, balls, golf balls, transport tools (eg transport shock absorbing grips, shock absorbing sheets), damping pallets , Shock absorbing damper, insulator, shock absorbing material for footwear, shock absorbing foam, shock absorbing material such as shock absorbing film, grip material, miscellaneous goods, toy, sole, sole, sole, sole of shoe, sole, sole , Sandals, suction cups, toothbrushes, floor materials, mats for gymnastics, electric tool members, agricultural equipment members, heat dissipating materials, transparent substrates, soundproofing materials, cushions Materials, electric cables, shape memory materials, medical gaskets, medical caps, medical caps, stoppers, gaskets, baby food, dairy products, medicines, sterile water, etc. filled in a bottle and then subjected to high temperature treatment such as boiling or high pressure steam sterilization Applications packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, fax legs, sewing machine legs, motor support mats, audio Precision equipment such as anti-vibration materials / OA equipment support member, heat-resistant packing for OA, animal cage, beaker, laboratory equipment such as beaker, measuring cylinder, cell for optical measurement, costume case, clear case, clear file, clear sheet, desk mat , As applications as fibers, for example, nonwovens, elastic nonwovens , 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 article according to the present invention can improve the impact resistance while maintaining its rigidity, and is excellent in the balance between the rigidity and the impact resistance. It can be suitably used for an exterior material, an outer plate material, a food container, and a beverage container.

  EXAMPLES The present invention will be more specifically described by way of the following examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

  In the following examples, physical properties of the olefin resin (β), terminally 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 Measurement of melting point (Tm) and heat of fusion ΔH was determined by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC 220, manufactured by SII), raise approximately 10 mg of sample from 30 ° C to 200 ° C at a heating rate of 50 ° C / min under a nitrogen atmosphere and hold 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 raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed in the second temperature rise was taken as a melting peak, and the temperature at which the melting peak appeared was determined as a 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 measurement of the glass transition temperature (Tg) was determined by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC 220, manufactured by SII), raise approximately 10 mg of sample from 30 ° C to 200 ° C at a heating rate of 50 ° C / min under a nitrogen atmosphere and hold at that temperature for 10 minutes did. Furthermore, it cooled to -100 degreeC with temperature-fall rate 10 degreeC / min, and after hold | maintaining for 5 minutes at the temperature, it heated up to 200 degreeC with the temperature increase rate of 10 degree-C / min. The glass transition temperature (Tg) is sensed as a change in specific heat causes the DSC curve to be bent and the baseline to be translated at the second temperature rise. The temperature at the intersection of the tangent of the baseline lower than this bending and the tangent of the point at which the slope is maximum at the bent portion was taken as the glass transition temperature (Tg).

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

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

(4) Ratio P of propylene polymer contained in olefin resin (β)
The ratio P was calculated from the ratio of the mass of the terminally 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) of the component whose peak value of the differential elution curve measured by cross-fractionation chromatograph (CFC) using ortho dichlorobenzene as a solvent is less than 65 ° C. The calculation method of the ratio E to is as follows.

Equipment: Cross-fractionation chromatography CFC2 (Polymer ChAR)
Detector (built-in): Infrared spectrophotometer IR ⁴ (Polymer ChAR)
Detection wavelength: 3.42 μm (2,920 cm ^-1 ); fixed sample concentration: 120 mg / 30 mL
Injection volume: 0.5mL
Cooling time: 1.0 ° C / min
Elution classification: 4.0 ° C interval (-20 ° C-140 ° C)
GPC column: Shodex HT-806 M × 3 (trade name, manufactured by Showa Denko)
GPC column temperature: 140 ° C.
GPC column calibration: monodispersed polystyrene (made by Tosoh Corporation)
Molecular weight calibration method: General-purpose calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (BHT added)
Flow rate: 1.0 mL / min.

In the calculation of the ratio E, the differential elution curve by the CFC measurement is peak-separated by the normal distribution curve, and the sum E _{(> 65 ° C.)} of the ratio (mass%) of the eluted components having the peak temperature above _{65 ° C.} , E = 100-E _{(> 65 ° C)} .

(6) Measurement of Intrinsic Viscosity [η] 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 sp sp was measured in an oil bath at 135 ° C. using a Ubbelode viscometer. After 5 ml of decalin was added to this decalin solution for dilution, the specific viscosity sp sp was measured in the same manner as described above. This dilution operation was further repeated twice, and the value of spsp / C when the concentration (C) was extrapolated to 0 was determined as the limiting viscosity [η] (unit: dl / g) (see the following formula).

    [.Eta.] = Lim (.eta.sp / C) (C.fwdarw.0).

(7) ¹³ C-NMR measurement ¹³ C-NMR measurement was carried out under the following conditions for the purpose of analyzing the composition ratio of ethylene and α-olefin of the polymer and confirming the stereoregularity of the terminally unsaturated polypropylene.

Device: AVANCE III 500 CryoProbe Prodigy nuclear magnetic resonance device (trade name, manufactured by Bruker Biospin)
Measurement kernel: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 μs)
Number of points: 64k
Measuring range: 250 ppm (-55 to 195 ppm)
Repeating time: 5.5 seconds Integration number: 512 times Measuring solvent: ortho-dichlorobenzene / benzene-d ₆ (4/1 v / v)
Sample concentration: ca. 60 mg / 0.6 mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 1.0 Hz)
Chemical shift standard: benzene-d ₆ (128.0 ppm).

(8) ¹ H-NMR Measurement For analysis of the terminal structure of the terminally unsaturated polypropylene, ¹ H-NMR measurement was performed under the following conditions.

Device: ECX400P nuclear magnetic resonance device (trade name: manufactured by Nippon Denshi)
Measuring kernel: ¹³ H (400 MHz)
Measurement mode: Single pulse Pulse width: 45 ° (5.25 μs)
Number of points: 32k
Measurement range: 20 ppm (-4 to 16 ppm)
Repeating time: 5.5 seconds Number of integrations: 64 Measurement solvent: 1,1,2,2-tetrachloroethane-d2
Sample concentration: ca. 60 mg / 0.6 mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 0.12 Hz)
Chemical shift standard: 1,1,2,2-tetrachloroethane (5.91 ppm).

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

Equipment: 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: ortho-dichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: Differential refractometer Flow rate: 1.0 mL / min Sample concentration: 0.15% (w / v)
Injection volume: 0.5mL
Sampling time interval: 1 second Column calibration: monodispersed polystyrene (manufactured by Tosoh Corporation).

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

(11) Measurement of isotactic pentad fraction (mm mm (%)) It is one of the indices of polymer stereoregularity, and the pentad fraction (mm mm (%)) whose microtacticity was examined is It computed from the peak intensity ratio of the < ¹³ > C-NMR spectrum assigned based on Macromolecules 8, 687 (1975) in propylene-type resin ((alpha)). ^{The 13} C-NMR spectrum was measured using an EX-400 (trade name, manufactured by JEOL Ltd.) as an apparatus, with reference to TMS, using an o-dichlorobenzene solvent at a temperature of 130 ° C. The isotactic pentad fraction was measured on terminally unsaturated polypropylene M-2.

(12) Measurement of the proportion of units derived from ethylene After dissolving 20 to 30 mg of the sample in 0.6 ml of a 1,2,4-trichlorobenzene / heavy benzene (mass ratio: 2/1) solution, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. The determination of propylene and ethylene was obtained from dyad chain distribution. In the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, EE = 1⁄2 (Sβδ + Sδδ) + 1⁄4Sγδ, and is determined according to the following formula.

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

(13) Measurement of flexural modulus (FM (MPa)) The flexural modulus was measured according to JIS K7171 under the following conditions.

Test specimen: 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 according to JIS K7111 under the following conditions to measure Charpy impact strength (kJ / m ² ).

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

  The notches are machined.

(Use reagent)
The toluene was purified using an organic solvent purification apparatus manufactured by GlassContour. As a toluene solution of aluminoxane, a 20% by mass methylaluminoxane / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd. was used. As triisobutyl aluminum, one manufactured by Tosoh Finechem Co., Ltd. was diluted with toluene (1.0 mol / L) and used.

Production Example 1
Step (A): Preparation of Terminally Unsaturated Polypropylene (M-2) In a fully nitrogen-substituted 1 L stainless steel autoclave, under nitrogen flow, 500 mL of toluene and a toluene solution of methylaluminoxane (1.5 mol / L) 0 .67 mL (1.0 mmol) was added. The autoclave was then closed and heated to 85 ° C. Next, while stirring the inside of the polymerization vessel at 600 rpm, the propylene partial pressure was increased to 0.3 MPa, and subsequently maintained at 85 ° C. The polymerization was initiated by injecting 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol / L) of dimethylsilylbis (2-methyl-4-finylindenyl) zirconium dichloride therein. The pressure was maintained while continuously supplying propylene gas, polymerization was carried out at 85 ° C. for 20 minutes, and then polymerization was stopped by injecting 5 mL of methanol. The resulting 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 14.9 g of terminally unsaturated polypropylene (M-2). The analysis results of the obtained polymer are shown in Table 2.

Step (B): Production of Olefin Resin (β-1) After putting 10.0 g of the above-mentioned terminally unsaturated polypropylene (M-2) and 500 ml of xylene in a sufficiently nitrogen-substituted 1 L glass reactor made of glass The temperature was raised to 97 ° C. to dissolve terminally unsaturated polypropylene (M-2). There, ethylene and 1-butene were continuously supplied at 120 liters / hr and 20.4 liters / hr, respectively, while stirring the inside of the polymerization vessel at 600 rpm, to saturate the liquid phase and the gas phase. Subsequently, with continuous supply of ethylene and 1-butene, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also described as iBu ₃ Al), represented by the following formula Toluene solution of the compound (0.0020 mol / L) 5.0 mL (0.01 mmol), then triphenyl carbenium tetrakis (pentafluorophenyl) borate (also described as Ph ₃ CB (C ₆ F ₅ ) ₄ ) in toluene 6.25 mL (0.025 mmol) of (4.0 mmol / L) was added, and polymerization was carried out under normal pressure at 97 ° C. for 40 minutes. The termination of the polymerization was carried out by adding a small amount of isobutanol. The resulting 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 dried under reduced pressure at 80 ° C. for 10 hours to obtain 35.2 g of an olefin resin (β-1). In addition, the compound shown by the following formula used as a catalyst was synthesize | combined by the well-known method. The analysis results of the olefin resin (β-1) are shown in Table 1.

Production Example 2
Production of Olefin-Based Resin (β′-1) An olefin-based resin (β′−) was produced in the same manner as in Production Example 1 except that the step (B) was carried out without the addition of the terminally unsaturated polypropylene (M-2). 1) was manufactured. 21.4 g of olefin resin (β'-1) was obtained. The analysis results of the olefin resin (β′-1) are shown in Table 1.

[Production Example 3]
Production of Olefin-Based Resin (β′-2) An olefin-based resin (β ′ ′ was produced in the same manner as in Production Example 1 except that the amount of 1-butene supplied was changed to 15 l / hr and step (B) was carried out. -2) was manufactured. 31.4 g of olefin resin (β'-2) was obtained. The analysis results of the olefin resin (β′-2) are shown in Table 1.

Production Example 4
Preparation of propylene-based homopolymer resin (α-h-1) (1) Preparation of solid titanium catalyst component Heat reaction of 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol at 130 ° C for 2 hours To obtain a homogeneous solution. In the solution, 21.3 g of phthalic anhydride was added, and the mixture was 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 added dropwise over 1 hour to 200 ml of titanium tetrachloride kept at -20 ° C. After completion of the dropwise addition, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when 110 ° C. was reached, 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours, It was made to react.

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

Here, the detection of the free titanium compound was performed by the following method. A 10 ml wash of the solid titanium catalyst component was collected by syringe and placed in a 100 ml branched Schlenk previously purged with nitrogen. The hexane was then dried under a stream of nitrogen and vacuum dried for an additional 30 minutes. Into this, 40 ml of ion exchange water and 10 ml of (1 + 1) sulfuric acid were added and stirred for 30 minutes. This aqueous solution is passed through filter paper and transferred to a 100 ml volumetric flask, followed by addition of 1 ml of concentrated H ₃ PO ₄ as a masking agent for iron (II) ions and 5 ml of 3% H ₂ O ₂ as a coloring reagent for titanium and ion exchange water The volume was made 100 ml. The volumetric flask was shaken and mixed, and after 20 minutes, absorbance at 420 nm was observed using a UV meter. The free titanium was washed away until this absorbance was no longer observed.

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

(2) Preparation of Prepolymerization Catalyst The solid titanium catalyst component (100 g), 39.3 mL of triethylaluminum, and 100 L of heptane were placed in a 200 L autoclave equipped with a stirrer. 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 prepolymerization catalyst.

(3) Main polymerization In a jacketed circulating type tubular polymerizer with an internal capacity of 58 L, 40 kg / hour of propylene, 223 NL / hour of hydrogen, 0.54 g / hour of the catalyst slurry produced in (2) above as a solid catalyst component, Triethylaluminum was continuously supplied at 2.4 ml / hour and dicyclopentyldimethoxysilane at 0.84 ml / hour, and polymerization was carried out in the absence of a gas phase. The temperature of the tubular polymerization vessel was 70 ° C., and the pressure was 3.57 MPa / G.

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

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

Example 1
23 parts by mass of the olefin resin (β-1) prepared in Preparation Example 1, 57 parts by mass of the propylene homopolymer resin (α-h-1) prepared in Preparation Example 4, talc (trade name: JM-) 209, 20 parts by mass of Asada Powder Co., Ltd., 0.1 parts by mass of heat resistant stabilizer IRGANOX 1010 (trade name, manufactured by Ciba Geigy Co., Ltd.), 0.1 heat resistant stabilizer IRGAFOS 168 (trade name, manufactured by Ciba Geigy Co., Ltd.) 0.1 After mixing by mass with 0.1 mass part of calcium stearate with a tumbler, the mixture was melt-kneaded under the following conditions with a twin-screw extruder to prepare a pellet-like propylene resin composition. The pellet-like propylene-based resin composition was injection-molded by an injection molding machine under the following conditions to prepare test pieces. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

<Melting and kneading conditions>
Coaxial twin screw kneader: KZW-15 (trade name, manufactured by Technobel Co., Ltd.)
Kneading temperature: 190 ° C
Screw rotational speed: 500 rpm
Feeder speed: 40 rpm
<JIS small test piece / injection molding condition>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-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) prepared in Preparation Example 1 is changed to 20 parts by mass, and 57 parts by mass of the propylene homopolymer resin (α-h-1) prepared in Preparation Example 4 is changed to 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. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

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 The propylene-based resin composition was prepared in the same manner as in the above. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

Comparative Example 2
A propylene-based resin composition was prepared in the same manner as in Comparative Example 1 except that 23 parts by mass of the olefin-based resin (β'-1) produced in Production Example 2 was changed to 26 parts by mass. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

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 The propylene-based resin composition was prepared in the same manner as in the above. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

Comparative Example 4
A propylene-based 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. Physical properties of the obtained propylene-based resin composition are shown in Table 3.

  In Table 3, the value in the parenthesis of the olefin resin and the propylene resin means the mass part of the olefin resin or the propylene resin when the total of the olefin resin and the propylene resin is 100 parts by mass. It shows each.

Claims (8)

Propylene-based resin (α) 50 to 98 parts by mass and olefin-based resin (β) 2 to 50 parts by mass satisfying the following requirements (I) to (VI) other than the propylene-based resin (α) And a total of 100 parts by mass of the olefin resin (β)).
(I) The olefin resin (β) contains a graft type olefin polymer [R1] having a main chain made of an ethylene / α-olefin copolymer and a side chain made of a propylene polymer.
(II) When the proportion 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 peak value of the differential elution curve measured by a cross fractionation chromatograph (CFC) using ortho-dichlorobenzene as a solvent and having a peak value of less than 65 ° C. with respect to the olefin resin (β) When it does, the value a represented by a 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 amount of thermal xylene insoluble 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 propylene-based polymer according to claim 1, wherein the proportion of 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 the monomers contained in the olefin resin (β). Resin composition.   The propylene-based resin composition according to claim 1 or 2, wherein the isotactic pentad fraction (mmmm) of the propylene polymer constituting the 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 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 5000 to 100000. .   The weight average molecular weight of the said ethylene-alpha-olefin copolymer which comprises the principal chain of the said graft-type olefin polymer [R1] is in the range of 50000-200000, Propylene-based resin composition. It is a manufacturing method of the propylene system resin composition in any one of Claims 1-5,
The manufacturing method of the propylene resin composition which manufactures the said olefin resin ((beta)) by the method containing a following process (A) and a process (B).
(A) Polymerization of propylene in the presence of a catalyst for olefin polymerization containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilyl bisindenyl skeleton to produce a terminally unsaturated polypropylene Process,
(B) In the presence of a catalyst for olefin polymerization containing a bridged metallocene compound represented by the following formula [B], the terminally unsaturated polypropylene produced in the step (A), ethylene, and 3 to 20 carbon atoms A step of copolymerizing with at least one α-olefin selected from the group consisting of α-olefins of

(In 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, a hydrocarbon group, a silicon-containing group or a silicon-containing group The other hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than a silicon-containing group.
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 hetero atom-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 represent an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand which can be coordinated with a lone electron pair In the case where j is an integer of 1 to 4 and j is an integer of 2 or more, plural 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 of performing copolymerization at 90 ° C or more.   The molded object of the propylene resin composition in any one of Claims 1-5.

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