JP6666089B2 - Propylene resin composition and molded article - Google Patents

Description

  The present invention relates to a propylene-based resin composition having excellent transparency, and a molded article formed from the composition.

  2. Description of the Related Art As packaging containers for foods such as jelly, pudding, coffee, and the like (hereinafter, also referred to as food packaging containers), containers having excellent visibility of contents, that is, excellent transparency, have been conventionally required. As a raw material for a container having excellent transparency, a propylene-based resin composition having excellent heat resistance, rigidity and transparency is often used.

  In addition, food is often handled in a low-temperature environment during storage and distribution, so food packaging containers must have not only impact resistance at room temperature but also low-temperature impact resistance, that is, low-temperature impact resistance. Can be

  As a propylene-based resin composition having excellent impact resistance, a composition containing a propylene-ethylene block copolymer, a nucleating agent, and a low-density polyethylene resin or a linear low-density polyethylene resin is known (for example, Patent Reference 1).

  As a propylene-based resin composition having excellent impact resistance, there is known a composition comprising a propylene block copolymer and an ethylene-based resin and having specific physical properties (for example, see Patent Documents 2 and 3).

  Patent Document 4 discloses a propylene-based resin composition containing a specific polypropylene resin, a specific ethylene / α-olefin copolymer, and a nucleating agent, and a molded article or a container obtained from the composition. Are known.

  Conventionally, in order to manufacture a food packaging container having excellent functions such as an elastic modulus, it has been performed to add an ethylene resin to a propylene resin, but the composition obtained in this manner is a propylene resin. It is known that the transparency is inferior to that of the case of a single type of resin alone, and a highly transparent material containing an appropriate ethylene resin has been demanded.

JP 2001-26686 A JP 2002-187996 A JP 2002-187997 A International Publication No. 2010/074001

  The present invention has been made in view of the above-mentioned problems of the prior art, and when manufacturing molded articles including containers such as food packaging containers, not only is excellent in transparency, but also low-temperature impact resistance and rigidity. It is an object of the present invention to provide a propylene-based resin composition excellent in any of the above, and a molded article such as a container formed from the composition.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, a composition containing a specific polypropylene resin, a specific ethylene / α-olefin copolymer resin, and a specific olefin-based resin has the above problem. Have been found, and the present invention has been completed.

That is, the propylene-based resin composition of the present invention contains 57 to 80 parts by weight of a polypropylene resin (A) satisfying the following requirements (A1) to (A3), and ethylene / α-olefin satisfying the following requirements (B1) to (B3). 17 to 40 parts by weight of the polymer resin (B) and 3 to 20 parts by weight of the olefin resin (C) satisfying the following requirements (C1) to (C4) (provided that the polypropylene resin (A) and the ethylene / α-olefin (The total of the polymer resin (B) and the olefin-based resin (C) is 100 parts by weight), and 0.1 to 1.0 part by weight of a nucleating agent.
(A1) The viscosity η ^* (25 rad / s) of the polypropylene resin (A) measured at 210 ° C. with a rheometer is 100 to 1000 Pa · s.
(A2) The polypropylene resin (A) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 10 to 170 g / 10 minutes.
(A3) Assuming that the constituent units derived from all the monomers constituting the polypropylene resin (A) are 100 mol%, the content of the constituent units derived from propylene is more than 80 mol% and not more than 100 mol%.
(B1) The density of the ethylene / α-olefin copolymer resin (B) is 885 to 925 kg / m ³ .
(B2) The ethylene / α-olefin copolymer resin (B) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 0.1 to 100 g / 10 min.
(B3) When the constitutional units derived from all the monomers constituting the ethylene / α-olefin copolymer resin (B) are 100 mol%, the composition has more than 80 mol% and 99 mol% or less of ethylene-derived constitutional units.
(C1) The olefin resin (C) contains 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.
(C2) When the proportion of the propylene polymer contained in the olefin-based resin (C) is P% by weight, P is in the range of 5 to 60.
(C3) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165C, and the glass transition temperature (Tg) is in the range of -80 to -40C.
(C4) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g.

The insoluble amount of hot xylene in the olefin resin (C) is preferably less than 3.0% by weight.
When the constituent units derived from all the monomers constituting the olefin resin (C) are 100 mol%, the olefin resin (C) preferably has 20 to 80 mol% of the constituent units derived from ethylene.

Ratio of the component of the olefin-based resin (C) having a peak temperature of less than 65 ° C. in a differential elution curve measured by cross fractionation chromatography (CFC) using ortho-dichlorobenzene as a solvent to the olefin-based resin (C) Is preferably E weight%, the value a represented by the following relational expression (Eq-1) is preferably 1.4 or more.
a = (100−E) / P (Eq−1)
The propylene polymer constituting the side chain of the graft type olefin polymer [R1] of the olefin resin (C) preferably has an isotactic pentad fraction (mmmm) of 93% or more.

The weight average molecular weight of the propylene polymer constituting the side chain of the graft olefin polymer [R1] is preferably in the range of 5,000 to 100,000.
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 50,000 to 200,000.

  The olefin-based resin (C) has a phase separation structure composed of a sea phase formed by an amorphous component and an island phase formed by a crystalline component, and the average of the island phase in a transmission electron microscope image. Preferably, the diameter is in the range of 50 nm to 500 nm.

It is preferable that the proportion P weight% of the propylene polymer contained in the olefin resin (C) is in the range of 30 to 60 weight%.
MFR ratio between olefin resin (C) and ethylene / α-olefin copolymer resin (B) MFR (C) / MFR (B) (230 ° C.) is preferably 0.8 to 3.5.
The propylene-based resin composition of the present invention preferably has a tensile modulus of 900 to 1400 MPa.
The molded article of the present invention is formed from the above propylene-based resin composition.

  The propylene-based resin composition of the present invention is excellent not only in transparency but also in low-temperature impact resistance and rigidity when a molded article such as a food packaging container is manufactured.

It is the graph which showed ratio E (weight%) with respect to the total amount of olefinic resin (C), ratio P (weight%), and a value. 4 is a graph showing the relationship between the elastic modulus and the Charpy strength of each test piece produced in the examples and comparative examples.

Next, the present invention will be specifically described.
The propylene-based resin composition of the present invention contains a specific polypropylene resin (A), an ethylene / α-olefin copolymer resin (B), and an olefin-based resin (C).

(Polypropylene resin (A))
The propylene-based resin composition of the present invention contains a polypropylene resin (A) satisfying the following requirements (A1) to (A3). Hereinafter, the polypropylene resin (A) satisfying the requirements (A1) to (A3) is also simply referred to as a polypropylene resin (A).
(A1) The viscosity η ^* (25 rad / s) of the polypropylene resin (A) measured at 210 ° C. with a rheometer is 100 to 1000 Pa · s.
(A2) The polypropylene resin (A) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 10 to 170 g / 10 minutes.
(A3) Assuming that the constituent units derived from all the monomers constituting the polypropylene resin (A) are 100 mol%, the content of the constituent units derived from propylene is more than 80 mol% and not more than 100 mol%.

(Requirements (A1))
The viscosity η ^* (frequency: 25 rad / s) of the polypropylene resin (A) measured at 210 ° C. with a rheometer is 100 to 1000 Pa · s, preferably 100 to 700 Pa · s. The viscosity η ^* is a temperature measured at a temperature of 210 ° C., which is a representative value in a range (about 170 to 240 ° C.) suitable for molding the propylene-based resin composition of the present invention. When A1) is satisfied, the moldability of the propylene-based resin composition tends to be excellent.

(Requirement (A2))
The polypropylene resin (A) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 10 to 170 g / 10 minutes, preferably 10 to 130 g / 10 minutes, More preferably, it is 10 to 100 g / 10 minutes.

  When the MFR of the polypropylene resin (A) exceeds the above range, the impact resistance of a molded article such as a container obtained from the propylene-based resin composition of the present invention is inferior, and the MFR of the polypropylene resin (A) falls within the above range. If it is lower than this, the flowability of the resin when producing a molded article such as a container using the propylene-based resin composition of the present invention is inferior, and it becomes difficult to produce a thin molded article.

  The MFR of the polypropylene resin (A) can be adjusted to an arbitrary MFR by adjusting production conditions such as using hydrogen as a chain transfer agent during polymerization. In addition to the above methods, the MFR can be adjusted by melt-kneading the polypropylene resin obtained by polymerization in the presence of an organic peroxide. The MFR of the polypropylene resin obtained by polymerization is increased by performing a melt-kneading process in the presence of an organic peroxide, and the addition of the organic peroxide during the melt-kneading process in the presence of the organic peroxide is performed. The MFR can be further increased by increasing the amount.

(Requirements (A3))
When the constitutional units derived from all the monomers constituting the polypropylene resin (A) are 100 mol%, the constitutional units derived from propylene are more than 80 mol% and 100 mol% or less, preferably 90 mol% or more and 100 mol% or less. It is. Therefore, the polypropylene resin (A) is a propylene homopolymer or a propylene copolymer satisfying the requirements (A1) to (A3). When the polypropylene resin is a propylene copolymer, it must be a copolymer of propylene and at least one olefin monomer (a) selected from ethylene and α-olefins (excluding propylene). Is preferred. When the polypropylene resin is a copolymer of propylene and an olefin-based monomer (a), when the constituent units derived from all the monomers constituting the polypropylene resin (A) are 100 mol%, the composition derived from propylene is It is preferable that the unit is more than 80 mol% and less than 100 mol%, the constitutional unit derived from the olefin monomer (a) is more than 0 mol% to less than 20 mol%, and the constitutional unit derived from propylene is 90 mol% It is more preferably at least 100 mol%, and more preferably more than 0 mol% and 10 mol% or less of the structural unit derived from the olefin monomer (a).

Examples of the olefin-based monomer (a) include ethylene and α-olefins having 4 to 20 carbon atoms, and among them, ethylene and α-olefins having 4 to 10 carbon atoms are preferable.
The polypropylene resin (A) preferably satisfies at least one of the following requirements (A4) to (A6) in addition to the above requirements (A1) to (A3).

(Requirements (A4))
The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn of the polypropylene resin (A) measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1.5 to 7.0. It is preferably from 1.5 to 6.0, and more preferably from 1.5 to 5.5.

  When the Mw / Mn is within the above range, the transparency of the obtained propylene-based resin composition and the molded article obtained from the composition are excellent. When the Mw / Mn exceeds the above upper limit, the transparency is deteriorated and the haze is increased. Tend to be.

(Requirements (A5))
The mmmm (pentad fraction) of the polypropylene resin (A) is preferably 91 to 100%.

mmmm is, for example, as described in JP-A-2007-186664, the proportion of isotactic chains in pentad units in the molecular chain measured using ¹³ C-NMR, in other words, propylene. It is the fraction of propylene monomer units at the center of a chain of five meso-bonded consecutive monomer units, and can be calculated by the measurement method disclosed in the publication. The measurement conditions of ¹³ C-NMR are not particularly limited, but may be, for example, the measurement conditions described in Examples.

(Requirements (A6))
The half value width of the melting temperature (Tm) peak of the polypropylene resin (A) measured by a differential scanning calorimeter (DSC) is preferably 5.0 to 20.0 ° C.

  The half width of the Tm peak is an index of the stereoregularity distribution of the polypropylene resin (A), and when the half width is within the above range, the obtained propylene-based resin composition and a molded article formed from the composition Tends to be particularly small.

(Production method of polypropylene resin (A))
The method for producing the polypropylene resin (A) is not particularly limited, but usually, the polypropylene resin (A) can be produced by polymerizing propylene in the presence of a metallocene compound-containing catalyst or in the presence of a Ziegler-Natta catalyst. Further, when the polypropylene resin (A) is a copolymer of propylene and a small amount of the olefin monomer (a), a small amount of the olefin monomer (a ) (Excluding propylene). The polymerization may be performed by any of a liquid phase polymerization method such as a gas phase polymerization method, a solution polymerization method, and a suspension polymerization method, and each stage may be performed by a separate method. In addition, the reaction may be performed in any of a continuous system and a semi-continuous system, and each stage may be divided into a plurality of polymerization units, for example, two to ten polymerization units. Industrially, it is most preferable to carry out polymerization by a continuous method.

  The polypropylene resin (A) may be used after melt-kneading in the presence of an organic peroxide. In such a case, it is preferable to use 0.005 to 0.05 parts by weight of the organic peroxide based on 100 parts by weight of the polypropylene resin (A).

  The organic peroxide that can be used in the melt kneading treatment is not particularly limited, but may be benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl. -2,5-di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylper Oxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dikimyl peroxide, 2,5-di-methyl-2,5-di -(T-butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) B) Hexin-3, 1,3-bis- (t-butylperoxyisopropyl) benzene, t-butylkimyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, kimene Hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide, 2,5-di-methyl-2,5-di- (hydro Organic peroxides such as peroxy) hexane are exemplified. Among these organic peroxides, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are preferred.

  Further, as the polypropylene resin (A), two or more kinds of polypropylene resins are mixed so as to satisfy at least one of the above requirements (A1) to (A3), preferably further the above requirements (A4) to (A6). A polypropylene resin mixture obtained by the above method may be used.

(Ethylene / α-olefin copolymer resin (B))
The propylene-based resin composition of the present invention contains an ethylene / α-olefin copolymer resin (B) satisfying the following requirements (B1) to (B3). Hereinafter, the ethylene / α-olefin copolymer resin (B) satisfying the requirements (B1) to (B3) is also simply referred to as an ethylene / α-olefin copolymer resin (B).
(B1) The density of the ethylene / α-olefin copolymer resin (B) is 885 to 925 kg / m ³ .
(B2) The ethylene / α-olefin copolymer resin (B) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 0.1 to 100 g / 10 min.
(B3) When the constitutional units derived from all the monomers constituting the ethylene / α-olefin copolymer resin (B) are 100 mol%, the composition has more than 80 mol% and 99 mol% or less of ethylene-derived constitutional units.

  The ethylene / α-olefin copolymer resin (B) is not particularly limited as long as it satisfies the requirements (B1) to (B3), but is preferably ethylene and carbon from the viewpoint of excellent impact resistance and transparency. It is a copolymer obtained by copolymerizing an α-olefin having 3 to 20 atoms.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these α-olefins, α-olefins having 4 to 10 carbon atoms are preferable from the viewpoints of transparency, impact resistance, rigidity, and economy.

  The ethylene / α-olefin copolymer resin (B) can be produced, for example, by polymerization using a so-called single-site catalyst or a multi-site catalyst such as a Ziegler-Natta catalyst.

  Examples of the single-site catalyst include a catalyst containing a constrained geometry complex (so-called constrained geometry catalyst (CGC) catalyst), a metallocene compound-containing catalyst, and the like. When the ethylene / α-olefin copolymer resin (B) is polymerized using a single-site catalyst, a propylene-based resin composition having higher transparency tends to be obtained. There is. When an ethylene / α-olefin copolymer polymerized using a metallocene compound-containing catalyst is used, a propylene-based resin composition having better low-temperature impact resistance tends to be obtained.

  Examples of the method for producing the ethylene / α-olefin copolymer resin (B) using a single-site catalyst include, for example, the method described in paragraphs [0131] to [0167] of WO 2010/074001. No.

  The ethylene / α-olefin copolymer resin (B) is a so-called linear low-density polyethylene resin, and a commercially available resin can be used if the above requirements are satisfied. For example, it is commercially available as Evolu (registered trademark: manufactured by Prime Polymer Co., Ltd.), Sumikasen-L (registered trademark: Sumitomo Chemical Co., Ltd.), Novatec LL (registered trademark: Nippon Polyethylene Corporation), and the like. Anything that meets the requirements can be used.

(Requirements (B1))
The density of the ethylene / α-olefin copolymer resin (B) is 885 to 925 kg / m ³ , preferably 900 to 919 kg / m ³ .

  When the density of the ethylene / α-olefin copolymer resin (B) is lower than the above lower limit, the rigidity and transparency of a molded article such as a container obtained from the propylene-based resin composition of the present invention tend to be inferior. This is presumed to be because the crystallinity of the ethylene / α-olefin copolymer decreases and the difference in refractive index from the polypropylene resin (A) also increases.

  On the other hand, when the density of the ethylene / α-olefin copolymer resin (B) exceeds the above upper limit, the transparency of a molded article such as a container obtained from the propylene-based resin composition of the present invention tends to decrease. . This is presumably because the difference in the refractive index between the ethylene / α-olefin copolymer and the polypropylene resin (A) increases. That is, when the density range of the ethylene / α-olefin copolymer resin (B) is out of the above range, the transparency is deteriorated.

  The density of the ethylene / α-olefin copolymer resin (B) can be set to a desired value by adjusting the production conditions described later. For example, in the polymerization of the ethylene / α-olefin copolymer resin (B) to be described later, by changing the ratio of the feed amount of ethylene and α-olefin when polymerizing the ethylene / α-olefin copolymer, The density of the α-olefin copolymer resin (B) can be adjusted to a desired value. Specifically, it is possible to lower the density by increasing the feed amount of α-olefin with respect to the feed amount of ethylene, and to reduce the feed amount of α-olefin with respect to the feed amount of ethylene. This makes it possible to increase the density.

  The density of the ethylene / α-olefin copolymer resin (B) was determined by heat-treating the ethylene / α-olefin copolymer resin (B) at 120 ° C. for 1 hour and gradually cooling it to room temperature over 1 hour. A sample was used and measured by a density gradient tube method.

(Requirements (B2))
The ethylene / α-olefin copolymer resin (B) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 0.1 to 100 g / 10 minutes, and preferably It is 1 to 20 g / 10 minutes, more preferably 2 to 10 g / 10 minutes.

  When the MFR of the ethylene / α-olefin copolymer resin (B) falls below the lower limit, the molecular weight becomes high, so that the flowability of the resin when producing a molded article such as a container is inferior and the molded article is thinned. When the MFR of the ethylene / α-olefin copolymer resin (B) exceeds the above upper limit, the molecular weight is low and the energy absorbed by impact is low. A molded article such as a container obtained from the resin composition tends to have poor impact resistance.

  The MFR of the ethylene / α-olefin copolymer resin (B) can be set to a desired value by adjusting the production conditions described later. For example, in the polymerization of the ethylene / α-olefin copolymer resin (B) to be described later, the ethylene / α-olefin copolymer is obtained by changing the feed amount of hydrogen gas with respect to the feed amounts of ethylene and α-olefin during polymerization. The MFR of the resin (B) can be adjusted to a desired value. Specifically, it is possible to increase the MFR by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin during polymerization, and to increase the amount of hydrogen gas relative to the feed amount of ethylene and α-olefin. It is possible to lower the MFR by reducing the feed amount.

The viscosity η ^* (frequency: 25 rad / s) of the ethylene / α-olefin copolymer resin (B) measured at 210 ° C. with a rheometer is usually from 200 to 2400 Pa · s, preferably from 250 to 1500 Pa · s. . The viscosity η ^* is a temperature measured at a temperature of 210 ° C., which is a range suitable for molding the propylene-based resin composition of the present invention. Tends to be excellent.

(Requirements (B3))
When the constitutional units derived from all the monomers constituting the ethylene / α-olefin copolymer resin (B) are 100 mol%, the constitutional units derived from ethylene are more than 80 mol% and 99 mol% or less, preferably 90 mol% or less. It is not less than mol% and not more than 99 mol%. When the constituent units derived from all the monomers constituting the ethylene / α-olefin copolymer resin (B) are 100 mol%, the constituent units derived from α-olefin are preferably at least 1 mol% and less than 20 mol%. And more preferably 1 mol% or more and 10 mol% or less.

(Olefin resin (C))
The propylene-based resin composition of the present invention contains an olefin-based resin (C) satisfying the following requirements (C1) to (C4). Further, the olefin resin (C) may be composed of only one olefin polymer, or may be composed of two or more olefin polymers. The olefin-based resin (C) satisfying the requirements (C1) to (C4) is also simply described as an olefin-based resin (C).
(C1) The olefin resin (C) contains 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.
(C2) When the proportion of the propylene polymer contained in the olefin-based resin (C) is P% by weight, P is in the range of 5 to 60.
(C3) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165C, and the glass transition temperature (Tg) is in the range of -80 to -40C.
(C4) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g.

(Requirement (C1))
The olefin-based resin (C) contains a graft-type olefin-based polymer [R1] as an essential component. The graft olefin polymer [R1] is a graft copolymer having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer. In the present invention, the term "graft copolymer" is a polymer having one or more side chains bonded to a main chain.

  Since the graft-type olefin polymer [R1] has a structure in which a side chain made of a propylene polymer is chemically bonded to a main chain made of an amorphous or low-crystalline ethylene / α-olefin copolymer, The olefin resin (C) containing the graft-type olefin polymer [R1] exhibits higher compatibility with the polypropylene resin than the ethylene / α-olefin copolymer having a linear structure. For this reason, the olefin-based resin (C) functions as a compatibilizing agent for favorably dispersing the ethylene / α-olefin copolymer resin (B) in the polypropylene resin (A), and the propylene-based resin composition of the present invention is high. Transparency is secured, and an extremely excellent balance of physical properties can be exhibited in rigidity and low-temperature impact resistance.

  The olefin-based resin (C) can be used without any particular limitation as long as it contains the graft-type olefin-based polymer [R1] and satisfies the requirements (C2) to (C4). For example, a reactive functional group such as maleic acid, halogen, or a detachable metal is introduced into a polyolefin disclosed in JP-A-2009-227898, and an ethylene / α-olefin-based copolymer chain and crystalline propylene are introduced. A resin produced by a method of causing a coupling reaction of a polymer chain may be used, and a polymerization catalyst described in JP-A-2001-527589, WO 2013/061974, and JP-A-2014-214204 may be used. Olefin including a branched olefin copolymer having a main chain composed of a copolymer of ethylene and α-olefin obtained by using the above and a side chain derived from a crystalline propylene polymer having a vinyl group at one end. A resin may be used.

  In particular, there are few by-products and residual substrates that cause coloring, off-flavors, contamination by eluting components, and the like, and are economically excellent. An olefin resin containing a branched olefin copolymer having a chain and a side chain derived from a crystalline propylene polymer containing a vinyl group at one end is preferable. Furthermore, since the olefin resin (C) obtained by the production method described below contains the graft-type olefin polymer [R1] in a high content, it exhibits excellent physical properties balance of transparency, rigidity and low-temperature impact resistance. This is a preferred embodiment.

  Further, since the olefin resin (C) contains the graft-type olefin polymer [R1] having the above structure, a general ethylene-based elastomer (for example, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / Octene copolymer), which is characterized by less stickiness and excellent handleability of product pellets.

As described above, the graft-type olefin polymer [R1] is a graft copolymer having a main chain and a side chain. In the present invention, the main chain and the side chain of the graft-type olefin polymer [R1] preferably satisfy the following requirements (i) to (iv).
(I) a main chain comprising a constituent unit derived from ethylene and at least one constituent unit derived from an α-olefin having 3 to 20 carbon atoms, and the constituent unit derived from the α-olefin; Is in the range of 10 to 50 mol% when the constitutional units derived from all the monomers constituting the main chain are 100 mol%.
(Ii) The main chain is derived from an ethylene / α-olefin copolymer having a weight average molecular weight of 50,000 to 200,000.
(Iii) The side chain consists essentially of a structural unit derived from propylene.
(Iv) The side chain is derived from a propylene polymer having a weight average molecular weight of 5,000 to 100,000.

Hereinafter, these requirements (i) to (iv) will be specifically described.
[Requirement (i)]
The main chain of the graft-type olefin polymer [R1] is composed of an ethylene / α-olefin copolymer, and the graft-type olefin polymer [R1] has low flexibility and low-temperature characteristics required as a modifier. It is the part that bears the characteristics. In order to ensure such properties, the main chain of the graft-type olefin-based polymer [R1] has a structural unit derived from ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. And olefin-derived structural units.

  Specific examples of the α-olefin having 3 to 20 carbon atoms copolymerized with ethylene in the ethylene / α-olefin copolymer include propylene, 1-butene, 2-methyl-1-propene and 2-methyl -1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl- 1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl Examples thereof include 1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

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

  The proportion of the constituent units derived from ethylene in the main chain of the graft-type olefin polymer [R1] is 50 to 90% by mole, preferably 100 to 90% by mole, assuming that the constituent units derived from all the monomers constituting the main chain are 100% by mole. It is in the range of 60 to 90 mol%. The ratio of the constituent unit derived from the α-olefin is in the range of 10 to 50% by mole, preferably 10 to 40% by mole, assuming that the constituent units derived from all the monomers constituting the main chain are 100% by mole.

  The relationship between the ratio of the constituent units derived from ethylene and the α-olefin and the glass transition temperature (Tg) differs depending on the type of the α-olefin used, but the range of the glass transition temperature (Tg) described in the requirement (C3) is achieved. In doing so, the proportion of constituent units derived from ethylene and α-olefin in the main chain of the graft-type olefin polymer [R1] is preferably within the above range.

  When the proportion of the constituent units derived from ethylene and α-olefin in the main chain is within the above range, the olefin resin (C) becomes rich in flexibility and excellent in low-temperature characteristics. Is excellent in low-temperature impact resistance. On the other hand, when the constituent unit derived from α-olefin is less than 10 mol%, the obtained olefin-based resin becomes a resin inferior in flexibility and low-temperature characteristics. Therefore, the propylene-based resin composition containing the resin has low impact resistance at low temperatures. May be inferior.

  The molar ratio of the constituent units derived from ethylene and α-olefin in the main chain can be adjusted by controlling the ratio between the concentration of ethylene and the concentration of α-olefin to be present in the polymerization system in the step of producing the main chain. .

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

[Requirement (ii)]
The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] is in the range of 50,000 to 200,000. In the propylene resin composition of the present invention, the weight average molecular weight is preferably in the range of 80,000 to 200,000 in order to improve moldability (flowability) while maintaining mechanical strength. The weight average molecular weight is a polyethylene equivalent weight average molecular weight determined by gel permeation chromatography (GPC).

  When the weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] is within the above range, the propylene-based resin composition containing the olefin-based resin (C) has a high proofness. There is a tendency for a better balance of impact, stiffness and toughness. On the other hand, if the weight average molecular weight is less than 50,000, the impact resistance and toughness decrease, and if the weight average molecular weight is more than 200,000, poor dispersion in the polypropylene resin (A) occurs, making it difficult to obtain a desired physical property balance. There are cases.

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

  The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain is, for example, to analyze the ethylene / α-olefin copolymer when produced under conditions not containing the terminal unsaturated polypropylene described below, Is determined by analyzing the olefin resin (C) and subtracting the effects derived from terminally unsaturated polypropylene and side chains.

[Requirements (iii)]
The side chain of the graft-type olefin polymer [R1] is substantially composed of propylene-derived constituent units. The side chain of the graft-type olefin-based polymer [R1] is a propylene polymer having an isotactic regularity consisting essentially of structural units derived from propylene.

  A propylene polymer substantially consisting of propylene-derived structural units is a homopolymer or copolymer mainly containing propylene-derived structural units in all the monomer-derived structural units, in a range that does not impair its role and characteristics. Structural units derived from other monomers, for example, a polymer which may contain a structural unit derived from at least one monomer selected from α-olefins other than ethylene and propylene, preferably, the propylene polymer Is a polymer in which the ratio of the constituent units derived from propylene is 99.5 to 100% by mole, when the constituent units derived from all the monomers contained in are contained in 100 mol%. In the case of a copolymer, it is preferable that a constituent unit derived from at least one monomer selected from α-olefins other than ethylene and propylene is contained in an amount of 0.05 mol% or less.

More preferably, the side chain of the graft-type olefin polymer [R1] is a propylene polymer chain having an isotactic pentad fraction (mmmm) of 93% or more.
Since the side chain of the graft-type olefin polymer [R1] has the above characteristics, the side chain exhibits crystallinity and has a melting point. The fact that the side chain of the graft type olefin polymer [R1] is a high melting point isotactic poly (propylene) polymer increases the compatibility of the olefin resin (C) with the polypropylene resin (A). . For this reason, the obtained propylene-based resin composition maintains good rigidity and hardness while exhibiting good impact resistance.

  The graft-type olefin polymer [R1] is obtained by, for example, copolymerizing ethylene and an α-olefin with the terminally unsaturated polypropylene produced in the step (P1) in the production step (P2) of the olefin resin (C) described below. Can be obtained. That is, the composition and stereoregularity of the terminal unsaturated polypropylene correspond to the side chain composition and stereoregularity of the graft-type olefin polymer [R1]. Therefore, the composition and stereoregularity of the terminally unsaturated polypropylene produced in the step (P1) are calculated using a known method, and the composition and stereoregularity are calculated based on the side chain composition and the graft-type olefin polymer [R1]. It can be defined as stereoregularity.

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

  When the weight average molecular weight of the propylene polymer constituting the side chain of the graft-type olefin polymer [R1] is within the above range, the compatibility between the polypropylene resin (A) and the olefin resin (C) increases, and The impact resistance and elongation at break of the propylene-based resin composition containing the resin (A) and the olefin-based resin (C) are well exhibited, and the fluidity during injection molding is also improved.

  When the weight average molecular weight of the propylene polymer constituting the side chain of the graft-type olefin polymer [R1] is smaller than 5,000, the interface strength with the polypropylene resin (A) is weakened, and the elongation and resistance of the propylene resin composition to elongation and resistance are reduced. Impact properties may be reduced.

  If the weight average molecular weight of the propylene polymer constituting the side chain of the graft-type olefin polymer [R1] is larger than 100,000, the fluidity during molding of the resin composition containing the olefin resin (C) becomes poor. , Which may cause deterioration of workability. Further, the compatibility between the polypropylene resin (A) and the olefin resin (C) is reduced, and the tensile elongation and impact resistance of the propylene resin composition containing the polypropylene resin (A) and the olefin resin (C) are reduced. When it is reduced, the surface hardness of a molded article obtained from the propylene-based resin composition may be reduced.

The weight average molecular weight of the propylene polymer constituting the side chain can be determined by, for example, the weight average molecular weight of the terminally unsaturated polypropylene produced in the step (P1) in the same manner as described in “Requirement (iii)” above. It can be obtained by measuring in. For example, the weight average molecular weight in terms of polypropylene of the terminal unsaturated polypropylene determined by gel permeation chromatography (GPC) can be used as the weight average molecular weight of the propylene polymer constituting the side chain.
As a method of adjusting the weight average molecular weight of the propylene polymer constituting the side chain, for example, a method of adjusting the polymerization temperature and the polymerization pressure in the production step (P1) described later is exemplified.

(Requirements (C2))
When the ratio of the propylene polymer contained in the olefin-based resin (C) (hereinafter, also referred to as ratio P) is P% by weight, P is in the range of 5 to 60% by weight, preferably 30 to 60% by weight. , More preferably 45 to 55% by weight.

When the proportion P is in the above range, the compatibility of the propylene polymer in the olefin resin (C) increases, and the propylene resin composition containing the olefin resin (C) has good impact resistance and elongation at break. Is expressed in When the proportion P is less than 5, the compatibility of the propylene polymer in the olefin resin (C) is low, and the obtained propylene resin composition may not exhibit good physical properties in impact resistance and elongation at break. . When the proportion P is larger than 60, the resulting propylene-based resin composition does not exhibit good physical properties in low-temperature impact resistance and elongation at break due to a small relative content of the ethylene / α-olefin copolymer. There is.
Here, the propylene polymer contained in the olefin-based resin (C) includes, for example, a propylene polymer side chain incorporated in the main chain and a propylene polymer not incorporated in the main chain in a polymerization step (P2) described later. Shows the sum of

The ratio P is determined, for example, from the ratio of the weight of the terminally unsaturated polypropylene used in the polymerization step (P2) described below and the weight of the obtained olefin-based resin (C).
The terminal unsaturated polypropylene means a polypropylene having an unsaturated terminal represented by the following terminal structures (I) to (IV). “Poly” in the terminal structures (I) to (IV) indicates a bonding position between the terminal structure and a propylene polymer molecular chain other than the terminal structure.

The ratio of unsaturated terminals in the terminal unsaturated polypropylene is usually 0.1 to 10 per 1000 carbon atoms, and more preferably 0.4 to 5.0. Furthermore, the unsaturated terminal ratio represented by the terminal structure (I) generally called terminal vinyl is generally in the range of 0.1 to 2.0 per 1,000 carbon atoms.

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

  For example, in the case of the terminal structure (I), assuming that the integral value A of δ 4.9 to 5.1 (2H) and the total integral value derived from the propylene polymer are B, the terminal structure (I) per 1000 carbon atoms The ratio is obtained by the formula of 1000 × (A / 2) / (B / 2). When calculating the ratio of other terminal structures, the ratio may be replaced with the integrated value of the peak assigned to each structure while paying attention to the ratio of hydrogen.

(Requirements (C3))
The olefin resin (C) has a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 120 to 165 ° C and a glass transition temperature (Tg) in the range of -80 to -40 ° C. .

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

  The temperature at which the above-mentioned melting peak appears, that is, the melting point (Tm) and the heat of fusion (ΔH) described below are determined by melting the sample once by DSC in a heating step, crystallizing the sample by a cooling step to 30 ° C. It is an analysis of an endothermic peak appearing in a heating step (heating rate: 10 ° C./min).

  The melting point (Tm) and heat of fusion (ΔH) observed in the above ranges are mainly due to the polypropylene side chains of the graft-type olefin polymer [R1] constituting the olefin resin (C). When the melting point (Tm) is in the above range, and more preferably, the heat of fusion (ΔH) is in the range described below, the olefin-based resin (C) can be well compatible with the polypropylene resin (A). As a result, the propylene-based resin composition containing the olefin-based resin (C) and the polypropylene resin (A) has a good balance of rigidity, heat resistance and toughness. As a method of adjusting the melting point (Tm) within the above range, a method of adjusting a polymerization temperature and a polymerization pressure in a production process (P1) described later is exemplified.

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

(Requirements (C4))
The intrinsic viscosity [η] of the olefin resin (C) measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g, preferably in the range of 1.0 to 4.0 dl / g, and more preferably. It is in the range of 1.0 to 3.0 dl / g. When the intrinsic viscosity [η] is in the above range, the propylene-based resin composition containing the olefin-based resin (C) has good rigidity and mechanical strength in addition to impact resistance, and further excellent molding. Also has workability.
The olefin resin (C) preferably satisfies at least one of the following requirements (C5) to (C10) in addition to the above requirements (C1) to (C4).

(Requirements (C5))
The amount of insoluble xylene in the olefin resin (C) is less than 3.0% by weight, preferably less than 2.5% by weight, and more preferably less than 2.0% by weight.
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 a hot press (180 ° C., heating 5 minutes, cooling 1 minute) and cut into small pieces. It is weighed in an amount of about 100 mg, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a closed container. Next, the screen is taken out and dried at 80 ° C. for 2 hours or more until a constant weight is obtained. The thermal xylene insoluble amount (% by weight) is represented by the following equation.
Thermal xylene insoluble amount (% by weight) = 100 × (W3-W2) / (W1-W2)
W1: Total weight of screen and sample before test, W2: Screen weight, W3: Total weight of screen and sample after test

  As described above, since the olefin-based resin (C) does not contain any or no amount of insoluble xylene, it can be well dispersed in the polypropylene resin (A), and as a result, the desired effect can be obtained. Is expressed. On the other hand, when the insoluble amount of hot xylene is 3% by weight or more, a molded article obtained from the propylene-based resin composition may have a poor appearance called "buts".

  As shown in the production method described below, by employing a method of directly obtaining a graft-type olefin-based polymer from the polymerization step, an olefin-based resin (C) having a heat xylene-insoluble component in the above range can be obtained.

(Requirements (C6))
When the constitutional units derived from all the monomers constituting the olefin-based resin (C) are 100 mol%, the constitutional units have a constitutional unit derived from ethylene of 20 to 80 mol%, preferably 30 to 80 mol%, more preferably 40 to 80 mol%. To 80 mol%, more preferably 40 to 75 mol%. When the constitutional unit derived from ethylene is in the above range, the olefin-based resin (C) is in a mode containing more ethylene / α-olefin copolymer, and the propylene-based resin containing the olefin-based resin (C) is included. The resin composition has good impact resistance and elongation at break.

(Requirements (C7))
The olefin-based resin (C) has a ratio (hereinafter also referred to as a ratio E) of a component having a peak temperature of less than 65 ° C. in a differential elution curve measured by cross fractionation chromatography (CFC) using ortho-dichlorobenzene as a solvent. When the value is E wt%, the value a (hereinafter, also referred to as a value) represented by the following relational expression (Eq-1) is 1.4 or more, and preferably 1.6 or more.
a = (100−E) / P (Eq−1)

The above-mentioned differential elution curve is obtained by differentiating the obtained cumulative elution curve when the elution temperature is in the range of −20 ° C. to 140 ° C. Furthermore, the component ratio of each elution peak can be obtained by separating each elution peak appearing in the differential elution curve into a normal distribution curve. Here, the ratio of soluble components below -20 ° C (the ratio of components that are not coated in the temperature rising elution fractionation (TREF) column even at -20 ° C in the cooling step of the CFC measurement) is expressed as E _(<-20 ° C ₎ weight. %, The sum of the proportions of the eluted components having a peak at -20 ° C or more and less than 65 ° C is E _(<65 ° C ₎ wt%, and the sum of the proportions of the eluted components having a peak at 65 ° C or more and 140 ° C or less is E ₍ ≧ _65). ° _C.) wt%, the component ratio that does not dissolve at 140 ° C. and E _{(> 140 ℃) wt%, E (<-20 ℃)} + E (<65 ℃) + E (≧ 65 ℃) + E (> 140 ℃) = 100 _Is defined as E = E _(<−20 ° C. ₎ + E _(<65 ° C. ₎ .

Usually, the olefin resin (C) is completely soluble in orthodichlorobenzene at 140 ° C., and a clear peak at 65 ° C. or higher where peak separation is easy can be detected. Therefore, E _{(> 140} ° C. ₎ = 0 Is defined as E = 100−E ₍ ≧ ₆₅ ° C. ₎ .

It is preferable to use an infrared spectrophotometer (detection wavelength: 3.42 μm) as the detector in the CFC measurement.
In the above-mentioned ratios E and P with respect to the total amount of the olefin-based resin (C), the total amount refers to only the resin obtained through a polymerization step described later. Is not included in the total amount.

  When the value a is in the above range, the olefin-based resin (C) corresponds to a graft-type olefin-based polymer [R1], that is, an ethylene / α-olefin copolymer having a propylene polymer site as a side chain. It indicates that the amount is included. The olefin-based resin (C) having the value a in the above range can be produced, for example, by a production method described later.

FIG. 1 shows the relationship between the ratio E (% by weight) and the ratio P (% by weight) and the value a.
In FIG. 1, the dotted line indicating the relationship of a = 1 indicates the case where the graft-type olefin-based polymer [R1] is not included, that is, the case of the mixture of the ethylene / α-olefin-based copolymer and the propylene polymer. On the other hand, as the production efficiency of the graft-type olefin polymer [R1] increases, the value of the ratio E to the ratio P decreases. As shown in FIG. 1, a large value of a indicates that the production efficiency of the graft-type olefin polymer [R1] is high. The olefin resin (C) of the present invention is characterized by having an a value of 1.4 or more.

  Generally, commercially available olefin elastomers used for polypropylene resin modifiers and the like are composed of ethylene / α-olefin copolymers (for example, ethylene / butene copolymers and ethylene / octene copolymers), and are derived from ethylene. It is a polymer in which the ratio of the constituent units is adjusted to about 90 mol% to 50 mol%. Therefore, the eluted component ratio E of the ordinary ethylene / α-olefin copolymer is substantially 100%.

(Requirements (C8))
The elastic modulus of the olefin resin (C) is 200 MPa or less, preferably 100 MPa or less, more preferably 50 MPa or less.

  Since the olefin-based resin (C) contains the graft-type olefin-based polymer [R1] and has abundant ethylene / α-olefin copolymer sites as its main chain, the flexibility resulting from the copolymer site is included. have. When the elastic modulus of the olefin-based resin (C) is within the above range, the propylene-based resin composition containing the olefin-based resin (C) exhibits good impact resistance. The elastic modulus is a tensile elastic modulus based on ASTM D638.

(Requirements (C9))
The olefin-based resin (C) has a phase separation structure composed of a sea phase formed by an amorphous component and an island phase formed by a crystalline component, and the average diameter of the island phase in a transmission electron microscope image is , 50 nm to 500 nm, and preferably 50 nm to 300 nm.

The observation as to whether or not it has the above-mentioned phase structure is performed, for example, as follows.
First, an olefin-based resin is charged into a kneading / molding evaluation apparatus and melt-kneaded at 200 ° C. and 60 rpm for 5 minutes. After preheating for 5 minutes using a hydraulic hot press molding machine set at 170 ° C. and then forming under pressure of 10 MPa for 1 minute, the olefin resin is cooled at 20 ° C. under pressure of 10 MPa for 3 minutes. To produce a press sheet having a predetermined thickness.

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

  According to such an observation method, the propylene-based polymer component is observed as a higher contrast since the intercrystalline amorphous portion of the lamellar structure formed by the component is selectively stained with osnic acid.

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

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

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

(Requirements (C10))
The heat of fusion ΔH at the melting peak (Tm) of the olefin resin (C) measured by differential scanning calorimetry (DSC) is in the range of 5 to 50 J / g, preferably in the range of 10 to 50 J / g.

  The melting peak (Tm) observed in the above range is a propylene polymer having a side chain composed of a propylene polymer of the graft-type olefin polymer [R1] and a propylene polymer having an unsaturated terminal contained in the olefin resin (C). And the fact that the heat of fusion (ΔH) is observed in the above range means that the side chain site of the graft-type olefin polymer [R1] contained in the olefin resin (C) has a considerable amount. Indicates that it contains. In the olefin-based resin (C) of the present invention, the presence of the propylene polymer side chain of the graft-type olefin-based polymer [R1] causes less stickiness and develops properties like a heat-resistant elastomer.

  On the other hand, when the heat of fusion (ΔH) is less than the above range, it means that the proportion of the propylene polymer side chain is small and, like the linear olefin elastomer, does not have heat resistance and is highly sticky. Further, the effect of modifying the polypropylene resin (A) is not sufficient. If the heat of fusion (ΔH) exceeds the above range, properties derived from the ethylene / α-olefin copolymer such as flexibility and low-temperature properties may be impaired.

The olefin-based resin (C) preferably further does not contain a substance that causes coloring, off-flavor, and contamination of the final product.
Specific examples of the substance causing the coloring, off-flavor and contamination of the final product include a hetero atom-containing compound, and the hetero atom-containing compound includes a chlorine atom, a halogen atom such as a bromine atom. Examples include compounds, compounds containing chalcogen atoms such as oxygen atom and sulfur atom, and compounds containing pnictogen compounds such as nitrogen atom and phosphorus atom. Specific examples of the compound containing an oxygen atom include maleic anhydride and a maleic anhydride reactant.

  Examples of the substance that causes the coloring, off-flavor, and contamination of the final product include metal atom-containing compounds, specifically, alkali metal-containing compounds such as sodium and potassium, and alkaline earth compounds such as magnesium and calcium. Metal-containing compounds.

  The content of the hetero atom-containing compound in the olefin-based resin (C) is preferably 1000 ppm or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less. The content of the metal atom-containing compound in the olefin-based resin (C) is preferably 1,000 ppm or less, more preferably 100 ppm or less, and still more preferably 10 ppm or less.

  The olefin-based resin (C) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature of 230 ° C., load of 2.16 kg) of preferably 0.1 to 100 g / 10 minutes, more preferably 1 to 100 g / 10 minutes. 20 g / 10 min.

The viscosity η ^* (frequency: 25 rad / s) of the olefin resin (C) measured at 210 ° C. with a rheometer is preferably 100 to 10000 Pa · s, and more preferably 500 to 5000 Pa · s.

(Method for producing olefin resin (C))
The olefin-based resin (C) is produced by, for example, a production method including the following steps (P1) and (P2).

(P1) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce a terminally unsaturated polypropylene. Step (P2) In the presence of an olefin polymerization catalyst containing a bridged metallocene compound [B] represented by the following general formula [B], the terminally unsaturated polypropylene produced in step (P1), ethylene, and carbon atoms Copolymerizing at least one α-olefin selected from α-olefins of Formulas 3 to 20

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

According to the above production method, an olefin resin (C) having a high content of the graft type olefin polymer [R1] is obtained, which is preferable.
Hereinafter, the steps (P1) and (P2) will be described in order.

[Step (P1)]
Step (P1) is a step of producing terminally unsaturated polypropylene which is a raw material for the polypropylene side chain of the graft-type olefin polymer [R1].

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

  The unsaturated terminal of the terminal unsaturated polypropylene means the terminal structures (I) to (IV) described above. The proportion occupied by the terminal structure (I) in the unsaturated terminal is usually at least 30%, preferably at least 50%, more preferably at least 60%. The proportion of the terminal structure (I) in the above-mentioned unsaturated terminals is the sum of the respective numbers of the 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 to the number of terminal structures is expressed as a percentage.

The transition metal compound [A] functions as a polymerization catalyst for producing terminally unsaturated polypropylene in combination with the compound [C] described below.
As a catalyst for olefin polymerization for producing terminally unsaturated polypropylene, Resconi, L .; JACS 1992, 114, 1025-1030, etc., have been known for a long time, but the side chain of the olefin-based copolymer [R1] may be an isotactic or syndiotactic terminally unsaturated polypropylene, more preferably isotactic. Tic, terminally unsaturated polypropylene is preferred.

  The transition metal compound [A] contained in the olefin polymerization catalyst used for producing such a polypropylene having a high stereoregularity and a high terminal unsaturated polypropylene content having a terminal structure (I) is disclosed in No. 100579, Japanese Translation of PCT International Publication No. 2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807 and JP-A-2008-285443. Can be.

  More specifically, as the transition metal compound [A], a compound selected from the group consisting of bridged bis (indenyl) zirconocenes or hafnocenes can be mentioned as a preferred example. More preferably, it is a dimethylsilyl bridged bis (indenyl) zirconocene or hafnocene. More preferably, it is a dimethylsilyl bridged bis (indenyl) zirconocene. By selecting zirconocene, generation of a long-chain branched polymer caused by an insertion reaction of terminally unsaturated polypropylene is suppressed, and the olefin-based resin (C) is contained. The propylene-based resin composition exhibits desired physical properties. On the other hand, when a large amount of the long-chain branched polymer is generated in the step (P1), the propylene-based resin composition containing the olefin-based resin (C) may impair physical properties such as rigidity.

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

The step (P1) can be performed by 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 (P1) is carried out by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; Of these polymerization solvents, hexane is preferred from the viewpoint of reducing the load of the post-treatment step. These polymerization solvents can be used alone or in combination of two or more.

  Further, the polymerization temperature in the step (P1) is usually in the range of 50 ° C to 200 ° C, preferably in the range of 80 ° C to 150 ° C, and more preferably in the range of 80 ° C to 130 ° C. By appropriately controlling the polymerization temperature, it becomes possible to obtain a terminally unsaturated polypropylene having a desired molecular weight and stereoregularity.

  The polymerization pressure in the step (P1) is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure. The polymerization reaction in the step (P1) can be performed by any of a batch system, a semi-continuous system, and a continuous system. In the present invention, among these, it is preferable to adopt a method in which monomers are continuously supplied to a reactor to perform copolymerization.

  The reaction time (average residence time when the copolymerization is carried out by a continuous method) in the step (P1) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually from 0.5 minutes to 5 hours, preferably from 0.5 minutes to 5 hours. 5 minutes to 3 hours.

  The polymer concentration in the step (P1) is 5 to 50% by weight, preferably 10 to 40% by weight during steady operation. It is preferably 15 to 50% by weight from the viewpoints of viscosity limitation in polymerization capacity, load of post-treatment step (desolvation) and productivity.

  The weight average molecular weight of the terminal unsaturated polypropylene produced in the step (P1) is preferably in the range of 5,000 to 100,000, more preferably 5,000 to 60,000, still more preferably 5,000 to 25,000. Range. By being a terminal unsaturated polypropylene having a weight average molecular weight in the above range, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin in the step (P2) described below. The efficiency of introduction into the chain is increased. On the other hand, if it exceeds the above range, the molar concentration of the terminally unsaturated polypropylene becomes relatively low, and the efficiency of introduction into the main chain becomes low. In addition, when it is lower than the above range, there is a practical problem such as a decrease in melting point.

  The molecular weight distribution (Mw / Mn) of the terminally unsaturated polypropylene produced in the step (P1) is 1.5 to 3.0, typically about 1.7 to 2.5. In some cases, a mixture of side chains having different molecular weights may be used.

The ratio of unsaturated terminals of the terminally unsaturated polypropylene produced in the step (P1) measured by ¹ H-NMR is usually 0.1 to 10 per 1000 carbon atoms, and more preferably 0.4 to 10 5.0. Further, the ratio of the unsaturated terminal having the terminal structure (I), that is, the so-called vinyl terminal amount is usually 0.1 to 2.0 per 1,000 carbon atoms, but preferably 0.4 to 2.0. In the range. When the amount of terminal vinyl is small, the amount of the terminal unsaturated polypropylene introduced into the main chain in the subsequent step (P2) is low, and the amount of the graft-type olefin polymer produced is small, so that the desired effect may not be obtained. .

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

[Step (P2)]
In the step (P2), the terminally unsaturated polypropylene produced in the step (P1), ethylene, a carbon atom This is a step of copolymerizing with at least one α-olefin selected from α-olefins of Formulas 3 to 20.

  In the step (P2), it is important to select a catalyst that exhibits sufficient activity at a high temperature and has high copolymerizability and high molecular weight. Since the terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and a sterically bulky structure, it is more difficult to polymerize than a linear vinyl monomer. Further, terminal vinyl polypropylene is not easily copolymerized under low temperature conditions at which a polymer is precipitated. For this reason, the catalyst is preferably required to exhibit sufficient activity at a polymerization temperature of 90 ° C. or higher, and to have the ability to make the main chain a desired molecular weight.

From such a viewpoint, in order to obtain an olefin-based resin (C) containing a high content of polypropylene, the crosslinked metallocene compound [B] is suitably used in the step (P2).
The bridged metallocene compound [B] is at least one selected from terminally unsaturated polypropylene produced in the step (P1) in combination with the compound [C] described below, ethylene, and an α-olefin having 3 to 20 carbon atoms. As an olefin polymerization catalyst for copolymerizing with an α-olefin.

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

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

[M2] The two ligands are linked by an aryl group-containing covalent cross-linking portion (hereinafter also referred to as a “cross-linking portion”) composed of a carbon atom or a silicon atom having an aryl group.
Hereinafter, the optionally substituted cyclopentadienyl group, substituted fluorenyl group, crosslinked portion, and other features of the bridged metallocene compound [B] will be sequentially described.

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

(Substituted fluorenyl group)
In the formula [B], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than the silicon-containing group, and include a hydrogen atom, a hydrocarbon group. Or a silicon-containing group is preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and the hydrogen atom, the hydrocarbon group and the silicon-containing group are Preferably, R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a hetero atom-containing group other than the silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group and 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; provided that “R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are all hydrogen atoms. "

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

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

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

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

When R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic or aromatic ring, the substituted fluorenyl group is represented by the following general formulas [II-C] to [VI-C]. Preferred examples include a group derived from the compound to be obtained.

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

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

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

(Other features of bridged metallocene compounds)
In the formula [B], Q can be coordinated by a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand or a lone electron pair. Represents a neutral ligand, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

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

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

(Exemplary Preferred Cross-Linked Metallocene Compound [B])
Specific examples of the crosslinked metallocene compound [B] are shown below in formulas [II-C] to [VI-C]. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [II-C], and octamethyltetrahydrodicyclopentafluorenyl refers to a group represented by the formula [III- C], and dibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [IV-C], and 1,1 ′, 3,6,8 , 8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VC], and includes 1,3,3 ', 6,6', 8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VI-C].

As the bridged metallocene compound [B], for example,
Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium Dichloride, diphenylmethylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium Dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (dimethyl Phenyl) -3,6-ditert-butylfluorenyl) c Niumujikurorido, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydro Cyclopentafluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl ) Hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadiene) Enyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6 -Di-tert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7 (Dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) hafnium dichloride Di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6 ', 8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluoride Oleenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclo Pentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl Hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclo Pentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6 ', 8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluoride Oleenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclo Pentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl Hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclo Pentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadiene) Enil) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6, 6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) ) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl Hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (Cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,

Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichlori Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, (M-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ( 2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichlori Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, (P-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ( 2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichloride, di (p tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert) -Butyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert- Butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl) Le-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentane Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3 6,7-tetra-tert-butylfluorenyl) hafnium dichloride,
Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- n-butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichloride, di (pn-butyl-phenyl) methyle (Cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene ( Cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Di-tert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,

Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexa Tyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7 -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p -Biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) ) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,3 , 6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (1-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl)- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl)- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluor Nyl) hafnium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride,
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3 , 6-Ditert-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium Dichloride, diphenylsilylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium Dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (dimethyl Phenyl) -3,6-ditert-butylfluorenyl) c Niumujikurorido, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butylfluorenyl) include hafnium dichloride.

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

  The above bridged metallocene compound can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in WO 01/27124 and WO 04/029062 by the present applicant.

The above bridged metallocene compounds [B] are used alone or in combination of two or more.
Step (P2) can be performed in solution (solution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin-based polymer is used. Is preferred.

The step of obtaining a polymerization reaction solution is a process in which an aliphatic hydrocarbon is used as a polymerization solvent, and the crosslinked metallocene compound [B], preferably, R ¹³ and R ¹⁴ bonded to Y ¹ in the above general formula [B] are converted to A phenyl group or a phenyl group substituted by an alkyl group or a halogen group, wherein R ⁷ and R ¹⁰ are ethylene and C 3 to C 3 in the presence of a metallocene catalyst containing a transition metal compound having an alkyl substituent. This is a step of obtaining a polymerization reaction solution of a copolymer of the α-olefin of No. 20 and the terminally unsaturated polypropylene produced in the step (P1).

  In the step (P2), the terminally unsaturated polypropylene produced in the step (P1) is fed in a solution or slurry to the reactor in the step (P2). The feeding method is not particularly limited. Even if the polymerization solution obtained in the step (P1) is continuously fed to the reactor in the step (P2), the polymerization solution in the step (P1) is temporarily buffered. After being stored in the tank, it may be fed to the step (P2).

  Examples of the polymerization solvent in the step (P2) 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 halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. These can be used alone or in combination of two or more. Further, the polymerization solvent in the step (P2) may be the same as or different from the polymerization solvent in the step (P1). Of these, aliphatic hydrocarbons such as hexane and heptane are preferred from an industrial viewpoint, and hexane is more preferred from the viewpoint of separation and purification from the olefin resin (C).

  Further, the polymerization temperature in the step (P2) is preferably in a range of 90 ° C to 200 ° C, and more preferably in a range of 100 ° C to 200 ° C. Such a temperature is preferred because the temperature at which the unsaturated terminal polypropylene dissolves well in aliphatic hydrocarbons such as hexane and heptane that are industrially preferably used as the polymerization solvent is 90 ° C. or higher. is there. A higher temperature is preferred from the viewpoint of improving the introduction amount of the polypropylene side chain. Further, it is preferable that the temperature be higher from the viewpoint of improving productivity.

  The polymerization pressure in the step (P2) is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure. The polymerization reaction may be performed in any of batch, semi-continuous and continuous methods. It can be carried out. Further, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, among these, it is preferable to adopt a method in which monomers are continuously supplied to a reactor to perform copolymerization.

  The reaction time (average residence time when the copolymerization is carried out by a continuous method) in the step (P2) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually from 0.5 minutes to 5 hours, preferably from 5 minutes to 5 hours. 5 minutes to 3 hours.

  The polymer concentration in the step (P2) during normal operation is 5 to 50% by weight, preferably 10 to 40% by weight. It is preferably 15 to 35% by weight from the viewpoints of viscosity limitation in polymerization capacity, post-treatment step (desolvation) load, and productivity.

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

[Compound [C]]
In the method for producing the olefin-based resin (C), a compound [C] described below is used together with the transition metal compound [A] and the cross-linked hametallocene compound [B] used as the olefin polymerization catalyst in the above-described steps (P1) and (P2). ] Is preferably used.

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

([C1] organometallic compound)
Specific examples of the [C1] organometallic compound used in the present invention include an organoaluminum compound represented by the following general formula (C1-a), a metal belonging to Group 1 of the periodic table represented by the following general formula (C1-b), Examples include a complex alkylated product with aluminum, and a dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by the general formula (C1-c). The [C1] organometallic compound does not include the [C2] organoaluminum oxy compound described below.

_{^{R a p Al (OR b)}} q H r Y s (C1-a)
In the general formula (C1-a), R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and Y is a halogen atom. Where p is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is a number of 0 ≦ s <3, and p + q + r + s = 3. )
M ³ AlR ^c ₄ (C1-b)
In the general formula (C1-b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms. )
R ^{d Re} M ⁴ (C1-c)
In the general formula (C1-c), R ^d and R ^e may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ⁴ is Mg , Zn or Cd.

Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).
_{^{R a p Al (OR b)}} 3-p (C-1a-1)
(Wherein, R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≦ p ≦ An organoaluminum compound represented by the formula:
_{^{R a p AlY 3-p (}} C-1a-2)
(Wherein, ^Ra represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number satisfying 0 <p <3). An organoaluminum compound represented by:
_{^{R a p AlH 3-p (}} C-1a-3)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2 ≦ p <3.)
_{^{R a p Al (OR b)}} q Y s (C-1a-4)
(Wherein, R ^a and R ^b may be the same or different from each other, represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p represents 0 <P ≦ 3, q is 0 ≦ q <3, s is a number satisfying 0 ≦ s <3, and p + q + s = 3).

More specifically, as the organoaluminum compound belonging to the general formula (C1-a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkyl aluminums such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri-4 Tri-branched alkyl aluminums such as -methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, tri 2-ethylhexyl aluminum;
Tricycloalkyl aluminums such as tricyclohexyl aluminum and tricyclooctyl aluminum;
Triarylaluminums such as triphenylaluminum and tolylaluminum;
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide;
Alkyl aluminum sesqui alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide;
R ^a _2.5 Al alkyl aluminum (wherein the partially alkoxylated with an average composition represented by (OR ^b) _0.5, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminium aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum 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;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

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

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

  In addition, as the [C1] organometallic compound, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, Butyl magnesium bromide, butyl magnesium chloride and the like can be used.

Further, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium is used as the above-mentioned organometallic compound [C1]. it can.
The [C1] organometallic compound as described above is used alone or in combination of two or more.

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

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

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

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

  The aluminoxane may contain a small amount of an organic metal component. After the solvent or unreacted organoaluminum compound is removed from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

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

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

  Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, hexadecane, octadecane, etc., and cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromides. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

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

  As the [C2] organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (III-C2) can also be mentioned.

(In the general formula (III-C2), R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{18 s} may be the same or different, and may be a hydrogen atom, a halogen atom, a carbon atom The number represents a hydrocarbon group of 1 to 10.)

  The organoaluminum oxy compound containing boron represented by the above general formula (III-C2) is obtained by converting an alkylboronic acid represented by the following general formula (IV-C2) and an organoaluminum compound under an inert gas atmosphere. In an inert solvent at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁹ -B (OH) ₂ (IV-C2)
(In Formula (IV-C2), R ¹⁹ represents the same group as R ¹⁷ in Formula (III-C2).)

  Specific examples of the alkylboronic acid represented by the general formula (IV-C2) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-boronic acid. Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid, and the like. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

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

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

([C3] Compound forming an ion pair by reacting with transition metal compound [A] or bridged metallocene compound [B])
The compound [C3] (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound [A] or the bridged metallocene compound [B] used in the present invention is disclosed in JP-A-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. And the like, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group or a fluorine) is used. And trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include a compound represented by the following general formula (V-C3).

(In the general formula (V-C3), R ²⁰ is H ^+, a ferrocenium cation having carbonium cations, oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a transition metal, R ²¹ ~ R ²⁴ may be the same or different and is an organic group, preferably an aryl group or a substituted aryl group.).

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

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

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

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

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

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

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

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

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VI-C3) or (VII-C3).

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

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

Specific examples of the borane compound as an example of the ionized ionic compound (compound [C3]) include, for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodeca hydride dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III) And the like.

Specific examples of the carborane compound as an example of the ionized ionic compound include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3- Dicarbanona borane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,3-dimethyl-1,3-dicarbanona borane, 7,8-dicarbaunde caborane, 2 , 7-Dicarboundecaborane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium L) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6- Carbadecaborate, tri (n-butyl) ammonium 6-carbumbadecaborate, tri (n-butyl) ammonium 7-carboundecaborate, tri (n-butyl) ammonium 7,8-dicarboundecaborate, tri ( (n-butyl) ammonium 2,9-dicarboundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-8- Ethyl-7,9-dicarboundeca Rate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, Anions such as tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate and tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salt;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III) Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca Metal carborane anions such as idolide-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) And the like.

  Heteropoly compounds that are examples of ionized ionic compounds include atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Compound. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadic acid, phosphomolybdotangustovanadic acid, germanomolybdo tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdniobic acid, and salts of these acids, but are not limited thereto. Examples of the salt include the above-mentioned acids, for example, metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Organic salts such as salts and triphenylethyl salts.

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

  The above-mentioned ionized ionic compounds (compounds that form an ion pair by reacting with [C3] transition metal compound [A] and cross-linked metallocene compound [B]) are used alone or in combination of two or more.

  When a [C2] organic aluminum oxy compound such as methylaluminoxane as a co-catalyst component is used in addition to the transition metal compound [A] and the bridged metallocene compound [B], a very high polymerization activity is exhibited for the olefin compound.

  In the organometallic compound [C1], the molar ratio (C1 / M) of the organometallic compound [C1] to the transition metal atom (M) in the transition metal compound [A] in the step (P1) is changed in the step (P2). )), The molar ratio (C1 / M) to the transition metal atom (M) in the bridged metallocene compound [B] is usually 0.01 to 100,000, preferably 0.05 to 50,000. Used in quantity.

  The organoaluminum oxy compound [C2] has a molar ratio (C2 / M) of the aluminum atom in the organoaluminum oxy compound [C2] to the transition metal atom (M) in the transition metal compound [A] in the step (P1). ), The molar ratio (C2 / M) to the transition metal atom (M) in the bridged metallocene compound [B] is usually 10 to 500,000, preferably 20 to 100,000 in the step (P2). Used in such amounts.

  The molar ratio (C3 / M) of the ionized ionic compound [C3] to the ionized ionic compound [C3] and the transition metal atom (M) in the transition metal compound [A] in the step (P1) is as follows: In (P2), the molar ratio (C2 / M) to the transition metal atom (M) (hafnium atom) in the bridged hafnocene compound [B] is usually 1 to 10, preferably 1 to 5 Used.

[Step (C)]
The method for producing the olefin-based resin (C) may include a step (C) for collecting the polymer generated in the step (P2), if necessary, in addition to the steps (P1) and (P2). This step is a step of separating the organic solvent used in the steps (P1) and (P2) to take out the polymer and convert it to a product form, and to produce an existing polyolefin resin such as solvent concentration, extrusion degassing, and pelletizing. There are no special restrictions if it is a process.

(Nucleating agent)
The propylene resin composition of the present invention further contains a nucleating agent in addition to the polypropylene resin (A), the ethylene / α-olefin copolymer resin (B), and the olefin resin (C).

  The nucleating agent contained in the propylene-based resin composition of the present invention is not particularly limited, but includes a sorbitol-based nucleating agent, a phosphorus-based nucleating agent, a metal carboxylate-based nucleating agent, a polymer nucleating agent, and an inorganic compound. Etc. can be used. As the nucleating agent, it is preferable to use a sorbitol nucleating agent, a phosphorus nucleating agent, and a polymer nucleating agent. The nucleating agents may be used alone or in combination of two or more.

  Examples of the sorbitol nucleating agent include nonitol 1,1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] (nonitol 1,2,3-trideoxy -4,6: 5,7-bis-O-[(4-propylphenyl) methylene]), 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di- (p-methylbenzylidene ) Sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol and the like.

  Examples of the phosphorus-based nucleating agent include sodium-bis- (4-tert-butylphenyl) phosphate, potassium-bis- (4-tert-butylphenyl) phosphate, and sodium-2,2′-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate, bis (2,4,8,10- And tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphin-6-oxide) aluminum hydroxide salt.

Examples of the carboxylic acid metal salt nucleating agent include aluminum pt-butyl benzoate, aluminum adipate, and sodium benzoate.
As the polymer nucleating agent, a branched α-olefin polymer is suitably used. Examples of the branched α-olefin polymer include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, and 4-methyl-1-pentene. A homopolymer of hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, or a copolymer thereof; Further, copolymers of these with other α-olefins may be mentioned. From the viewpoints of good transparency, low-temperature impact resistance, rigidity, and economy, a polymer of 3-methyl-1-butene is particularly preferable.

Examples of the inorganic compound include talc, mica, calcium carbonate and the like.
Among these nucleating agents, from the viewpoint of transparency, low-temperature impact resistance, rigidity and low odor, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O- [ (4-propylphenyl) methylene] and / or bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphospho It is preferable to use (syn-6-oxide) aluminum hydroxide salt.

  As the nucleating agent used in the present invention, commercially available products can be used. For example, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene Is commercially available under the trade name Millard NX8000 (Milliken), and ADK STAB NA-21 (trade name, manufactured by Adeka) is bis (2,4,8,10-tetra-t-butyl-6-). It is commercially available as a nucleating agent containing hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6-oxide) aluminum hydroxide salt as a main component.

  When the propylene-based resin composition of the present invention contains a nucleating agent, a molded article such as a container formed from the composition of the present invention tends to have excellent rigidity and transparency. This is presumably because the spherulite size of the crystals in the propylene-based resin composition is reduced and the irregular reflection of light is reduced, and the transparency is improved, and the crystallinity is increased to increase rigidity.

  When the content of the nucleating agent of the propylene-based resin composition is less than the following range, the effect of improving rigidity and transparency is insufficient, and when the content of the nucleating agent is more than the following range, further improving effect is obtained. Less and not economical.

(Propylene resin composition)
The propylene resin composition of the present invention contains a polypropylene resin (A), an ethylene / α-olefin copolymer resin (B), and an olefin resin (C). The content of each component of the propylene-based resin composition is usually defined as 100 parts by weight of the total of the polypropylene resin (A), the ethylene / α-olefin copolymer resin (B), and the olefin-based resin (C). Resin (A) 57 to 80 parts by weight, ethylene / α-olefin copolymer resin (B) 17 to 40 parts by weight, olefin resin (C) 3 to 20 parts by weight, preferably polypropylene resin (A) 62 To 75 parts by weight, 22 to 35 parts by weight of an ethylene / α-olefin copolymer resin (B), and 3 to 10 parts by weight of an olefin resin (C). The propylene-based resin composition further contains a nucleating agent, and the content is 100 weight% of the total of the polypropylene resin (A), the ethylene / α-olefin copolymer resin (B), and the olefin-based resin (C). Parts are 0.1 to 1.0 part by weight, preferably 0.1 to 0.4 part by weight.

  In addition, the propylene-based resin composition of the present invention may be appropriately neutralized, an antioxidant, a heat stabilizer, a weathering agent, a lubricant, an ultraviolet absorber, an antistatic agent, and an antiblocking agent as long as the object of the present invention is not impaired. Agents, anti-fog agents, anti-foaming agents, dispersants, flame retardants, antibacterial agents, additives such as optical brighteners, cross-linking agents, cross-linking assistants, degra agents (organic peroxides); coloring of dyes, pigments, etc. Other components such as agents may be included.

  When the propylene-based resin composition of the present invention contains other components, the total amount of the polypropylene resin (A) and the ethylene / α-olefin copolymer resin (B) is usually 100 parts by weight, and is usually 0.1 part by weight. 0001 to 10 parts by weight.

  Further, the propylene-based resin composition of the present invention preferably has a melt flow rate (MFR) (measuring temperature 230 ° C., load 2.16 kg) of 20 to 200 g / 10 minutes, and preferably 25 to 140 g / 10 minutes. More preferably, it is more preferably 30 to 80 g / 10 minutes. The above range is preferable because the fluidity when molding a molded article such as a container using the propylene-based resin composition is excellent.

  The MFR of the propylene-based resin composition is the melt flow rate (MFR) of the polypropylene resin (A) constituting the propylene-based resin composition (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg), or ethylene α -It can be adjusted by appropriately selecting the melt flow rate (MFR) of the olefin copolymer resin (B) (ASTM D-1238, measurement temperature 190 ° C, load 2.16 kg).

  In addition, other than the above-mentioned methods, when components are melted and kneaded with a kneader, adjustment can be made by coexisting an organic peroxide. That is, the MFR of the propylene-based resin composition can be increased by adding an organic peroxide during melt-kneading or increasing the amount of the organic peroxide during melt-kneading. The organic peroxide that can be used in the present invention is not particularly limited, but may be benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-peroxide. -Methyl-2,5-di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t- Butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dikimyl peroxide, 2,5-di-methyl-2,5 -Di- (t-butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) Xy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t-butyl kimyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, kimene Hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide, 2,5-di-methyl-2,5-di- (hydro Peroxy) hexane and the like. Among them, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferable. When an organic peroxide is used, it should be used in a range of 0.005 to 0.05 parts by weight based on 100 parts by weight of the total of the polypropylene resin (A) and the ethylene / α-olefin copolymer resin (B). Is preferred.

The propylene-based resin composition of the present invention preferably has a tensile modulus of 900 to 1400 MPa, more preferably 900 to 1200 MPa.
The tensile modulus of the propylene-based resin composition of the present invention can be determined by injection molding the composition using an injection molding machine having a mold clamping force of 40 tons at a cylinder temperature of 210 ° C. and a mold temperature of 40 ° C. It is measured using the obtained tensile modulus test piece. As a specific method for measuring the tensile modulus of the propylene-based resin composition, the method described in Examples described later can be used.

Propylene resin composition of the present invention, the Charpy impact strength was measured by the method described in Example, is preferably 1.5 kJ / m ² or more, more preferably 1.7kJ / m ² or more . The upper limit is not particularly limited, but is usually 4.0 kJ / m ² or less.

  In the propylene-based resin composition of the present invention, the haze measured by the method described in Examples is preferably 15% or less, more preferably 13% or less. There is no particular lower limit.

  When the tensile elastic modulus of the propylene-based resin composition of the present invention is within the above range, the molded body including a container such as a food packaging container is thinner than before, and has high rigidity even if it is reduced in weight, and a large load is applied. It is preferable because it does not easily deform even if it is applied.

  The propylene-based resin composition of the present invention mainly has a so-called sea-island structure in which the polypropylene resin (A) is a continuous phase, that is, a sea phase. The ethylene / α-olefin copolymer resin (B) mainly forms an island phase. For this reason, the propylene-based resin composition of the present invention can achieve both high rigidity and impact resistance. Further, the olefin-based resin (C) desirably exists at the interface between the polypropylene resin (A) and the ethylene / α-olefin copolymer resin (B), in which case the molded article becomes highly transparent.

(Viscosity ratio)
The propylene-based resin composition of the present invention has a ratio of the viscosity η ^* (frequency: 25 rad / s) of the ethylene / α-olefin copolymer resin (B) and the polypropylene resin (A) measured at 210 ° C. with a rheometer. (Viscosity of B / viscosity of A) is usually 2.0 to 6.0, preferably 2.0 to 5.5, and more preferably 2.5 to 5.0.

If it exceeds this range, the haze of the propylene-based resin composition deteriorates. On the other hand, if the ratio is less than this range, the MFR of the propylene-based resin composition becomes extremely low, which is not desirable.
Further, the propylene-based resin composition of the present invention has a viscosity η ^* (frequency: 25 rad / cm) of the olefin-based resin (C) and the ethylene / α-olefin copolymer resin (B) measured at 210 ° C. with a rheometer. The ratio (viscosity of C / viscosity of B) of s) is usually 1.0 to 4.4, preferably 1.0 to 4.0, more preferably 1.0 to 3.0. And particularly preferably from 1.0 to 2.0.

If it exceeds this range, the haze of the propylene-based resin composition may deteriorate.
The viscosity of each of the polypropylene resin (A), the ethylene / α-olefin copolymer resin (B), and the olefin resin (C) can be measured at a temperature of 210 ° C. and a frequency of 25 rad / s using a rheometer. .

When the propylene-based resin composition is molded, a phase structure in which an island phase formed from the ethylene / α-olefin copolymer resin (B) is dispersed in a sea phase formed from the polypropylene resin (A) is formed. When the ratio of the viscosity η ^* (frequency: 25 rad / s) of the olefin resin (C) and the ethylene / α-olefin copolymer resin (B) measured at 210 ° C. with a rheometer is within the above range, The olefin-based resin (C) is not dispersed alone in the sea phase formed from the polypropylene resin (A), and the olefin is present at the interface between the polypropylene resin (A) and the ethylene / α-olefin copolymer resin (B). The system resin (C) is disposed, and the transparency tends to be more excellent, which is preferable.

  When the propylene-based resin composition of the present invention is injection-molded, the island structure differs between the vicinity of the surface of the molded article and the inside of the molded article. Specifically, in a portion near the surface, the island structure becomes flat (a flat shape in which the depth direction of the formed body is short), and approaches a spherical shape inside the formed body. Since the island structure near the surface of the molded body is flat, light scattering in the portion is suppressed and the internal haze is reduced. Therefore, the molded article of the present invention is excellent in transparency. Further, by using a polymer obtained by a single-site catalyst as the polypropylene resin (A), the effect of reducing the internal haze can be further exhibited.

  Since the propylene-based resin composition of the present invention contains the above-described components in the above range, when manufacturing a molded article including a container such as a food packaging container, the same rigidity as the conventional, the same or the same as the conventional. It has the above low-temperature impact resistance, and is more excellent in transparency than before.

(MFR ratio)
The propylene-based resin composition of the present invention has an MFR ratio (MFR (C) / MFR (B)) of the olefin-based resin (C) and the ethylene / α-olefin copolymer resin (B) measured at 230 ° C. ) Is preferably from 0.8 to 3.5, more preferably from 0.8 to 2.5, and still more preferably from 0.8 to 1.5.

When the MFR ratio exceeds the above upper limit, the strength of a molded article obtained from the propylene-based resin composition is significantly reduced. Further, when the MFR ratio is lower than the lower limit described above, the haze becomes extremely high.
The method for producing the propylene-based resin composition of the present invention is not particularly limited. Examples of the production method include a method in which each component is melt-kneaded with a kneader to produce a propylene-based resin composition. Examples of the kneading machine include a single-screw kneading extruder, a multi-screw kneading extruder, a kneader, a Banbury mixer, and a Henschel mixer. Melt kneading conditions are not particularly limited as long as the molten resin is not degraded by shearing during kneading, heating temperature, heat generated by shearing, or the like. From the viewpoint of preventing the deterioration of the molten resin, it is effective to appropriately set the heating temperature or to add an antioxidant or a heat stabilizer.

  Various molded articles can be obtained by molding the propylene-based resin composition of the present invention according to a known molding technique. Molding techniques include, for example, injection molding, injection stretch blow molding, compression molding, injection compression molding, T-die film molding, stretched film molding, inflation film molding, sheet molding, calendar molding, air pressure molding, vacuum molding, pipe molding, irregular molding Extrusion molding, hollow molding, laminate molding and the like can be mentioned.

Examples of the molded article formed from the propylene-based resin composition of the present invention include containers, home electric parts, and daily necessities. Above all, a container is preferable from the viewpoint of impact resistance and rigidity.
The container of the present invention is formed from the propylene-based resin composition described above. Containers include packaging containers for liquid daily necessities such as hair washes, hairdressing agents, cosmetics, detergents, and disinfectants; food packaging containers for liquids such as soft drinks, water, and seasonings; solids such as jelly, pudding, and yogurt Food packaging containers; other chemical packaging containers; and industrial liquid packaging containers.

Above all, it is required to be thinner and lighter than before, and it can be suitably used as a food packaging container which is required to have excellent visibility of contents and low odor.
The container (for example, a food packaging container) formed from the propylene-based resin composition of the present invention is preferably obtained by injection molding or injection stretch blow molding.

As an injection molding method, molding can be performed by the following method using an injection molding machine, for example. First, a propylene-based resin composition is introduced into a hopper of an injection mechanism, and the propylene-based resin composition is fed into a cylinder heated to about 200 ° C. to 250 ° C., kneaded and plasticized to be in a molten state. The metal is closed at a high pressure and high speed (maximum pressure 700 to 1500 kg / cm ³ ) from a nozzle and cooled to 5 to 50 ° C., preferably 30 to 50 ° C. by cooling water or hot water and closed by a mold clamping mechanism. Inject into mold. This can be performed by cooling and solidifying the propylene-based resin composition injected by cooling from the mold, opening the mold with a mold clamping mechanism, and obtaining a molded product.

As the injection stretch blow molding, for example, a propylene-based resin composition is introduced into a hopper of an injection molding machine, and the resin is fed into a cylinder heated to about 200 ° C. to 250 ° C., kneaded, plasticized, and melted. I do. The metal is closed at a high pressure and high speed (maximum pressure 700 to 1500 kg / cm ³ ) from a nozzle at a temperature of 5 to 50 ° C., preferably 10 to 30 ° C. by cooling water or hot water and closed by a mold clamping mechanism. Injection molding is performed in a mold, where it is cooled for 1.0 to 3.0 seconds to form a preform. Immediately after that, the mold is opened, stretched and oriented in a vertical direction using a stretching rod, and further laterally blow-molded. And stretching to obtain a molded product.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
[Evaluation method]
The physical properties of the polypropylene resin (A), ethylene / α-olefin copolymer resin (B), olefin resin (C) and propylene resin composition were measured according to the methods described below.

(Method of measuring physical properties of polypropylene resin (A))
(1) viscosity η ^*
The viscosity η ^* was measured using a rheometer (PHYSICA MCR301 manufactured by Anton Paar Japan).
The measurement conditions were set as follows.
Sample: Press plate 28mmφ × 1mm
Measurement jig: plate-plate gap: 0.8 mm
Measurement temperature: 210 ° C
Measurement frequency: 25 rad / s

(2) Melt flow rate (MFR)
MFR was measured at 230 ° C. under a load of 2.16 kg according to ASTM D1238.

(3) Proportion of Structural Unit Derived from Propylene in Polypropylene Resin (A) The ratio (mol%) of the constituent unit derived from propylene in the polypropylene resin (A) was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum.
^{The 13} C-NMR spectrum was measured using an apparatus of EX-400 manufactured by JEOL Ltd., based on TMS, at a temperature of 130 ° C. and using an o-dichlorobenzene solvent.

(4) GPC measurement (Mn, Mw, Mw / Mn)
GPC analysis was performed under the following conditions for molecular weight analysis of the polymer. From the chromatogram obtained by GPC measurement, the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were determined, and the value of Mw / Mn was calculated.
Apparatus: Waters Alliance GPC 2000 type column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (all manufactured by Tosoh Corporation, inner diameter 7.5 mm x length 30 cm)
Column temperature: 140 ° C
Mobile phase: orthodichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: Differential refractometer Flow rate: 1.0 mL / min
Sample concentration: 0.15% (w / v)
Injection volume: 0.5 mL
Sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).

(5) Stereoregularity Pentad fraction (mmmm: [%])
The pentad fraction (mmmm,%) of the polypropylene resin (A) was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Macromolecules 8,687 (1975). ^{The 13} C-NMR spectrum was measured using an apparatus of EX-400 manufactured by JEOL Ltd., based on TMS, at a temperature of 130 ° C. and using an o-dichlorobenzene solvent.

(6) Stereoregularity distribution DSC half width The half width of the melting temperature (Tm) peak of the polypropylene resin (A) was determined by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter [SDC RDC220], about 10 mg of the sample was heated from 30 ° C. to 230 ° C. at a rate of 500 ° C./min in a nitrogen atmosphere, and kept at that temperature for 10 minutes. Further, the temperature was lowered to 50 ° C. at a temperature lowering rate of 10 ° C./min, kept at that temperature for 5 minutes, and then raised to 190 ° C. at a temperature increasing rate of 10 ° C./min. The endothermic peak observed at the time of the second temperature rise was defined as a melting peak, and the temperature was determined as a melting temperature (Tm), and the half width of the peak was derived.

(Method for measuring physical properties of ethylene / α-olefin copolymer resin (B))
(7) Density The density was measured by the following method.
The strand obtained when measuring the melt flow rate of the ethylene / α-olefin copolymer resin (B) at a measurement temperature of 190 ° C. under a load of 2.16 kg (ASTM D-1238) is heat-treated at 120 ° C. for 1 hour. The density was measured by the density gradient tube method using what was gradually cooled to room temperature over 1 hour as a sample.

(8) Melt flow rate (MFR)
MFR was measured by the same method as in the above (2).

(9) viscosity η ^*
The viscosity η ^* was measured by the same method as in the above (1).

(10) Ratio of Structural Unit Derived from Ethylene in Ethylene / α-Olefin Copolymer Resin (B) The ratio (mol%) of the structural unit derived from ethylene in the ethylene / α-olefin copolymer resin (B) is ^It was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum.
^{The 13} C-NMR spectrum was measured using an apparatus of EX-400 manufactured by JEOL Ltd., based on TMS, at a temperature of 130 ° C. and using an o-dichlorobenzene solvent.

(Method for measuring physical properties of olefin resin (C) and terminally unsaturated polypropylene)
(11) ¹³ ratio of C-NMR constituent units derived from ethylene measured in the polymer, alpha-olefin proportion of the structural unit derived from, and terminally unsaturated polypropylene stereoregularity object of confirmation, ¹³ C by: -NMR measurements were performed. Apparatus: Bruker BioSpin AVANCE III500 CryoProbe Prodigy type nuclear magnetic resonance apparatus, measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45 ° (5.00 μsec), number of points: 64 k , Measurement range: 250 ppm (-55 to 195 ppm), repetition time: 5.5 seconds, integration frequency: 512 times, measurement 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).

(12) ¹ H-NMR Measurement In order to analyze the terminal structure of the terminal unsaturated polypropylene, ¹ H-NMR measurement was carried out under the following conditions. Apparatus: JEOL ECX400P type nuclear magnetic resonance apparatus, measurement nucleus: ¹³ H (400 MHz), measurement mode: single pulse, pulse width: 45 ° (5.25 μsec), number of points: 32 k, measurement range: 20 ppm (− 4 to 16 ppm), repetition time: 5.5 seconds, number of integration: 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).

(13) GPC measurement (Mn, Mw, Mw / Mn)
GPC measurement was performed by the same method as in the above (4).

(14) Measurement of Ratio P of Propylene Polymer Contained in Olefin Resin (C) to Olefin Resin (C) As described above, the weight of the terminal unsaturated polypropylene used in step (P-2) was obtained. It was calculated from the weight ratio of the olefin resin (C).

(15) Measurement of Cross Separation Chromatography (CFC) The ratio E of a component having a peak value of a differential elution curve measured by cross separation chromatography (CFC) using orthodichlorobenzene as a solvent of less than 65 ° C. to the olefin-based resin E and The method of calculating the ratio (wt%) of the components soluble in ortho-dichlorobenzene at 50 ° C. or lower has been described in the requirements (III) and (XI). It is as follows.
Device: cross fractionation chromatograph CFC2 (Polymer ChAR), detector (internal): infrared spectrophotometer IR ⁴ (Polymer ChAR), detection wavelength: 3.42μm (2,920cm-1); fixed, sample concentration: 120 mg / 30 mL, injection volume: 0.5 mL, cooling time: 1.0 ° C./min, elution category: 4.0 ° C. intervals (−20 ° C. to 140 ° C.), GPC column: Shodex HT-806M × 3 tubes (Showa Denko GPC column temperature: 140 ° C, GPC column calibration: monodisperse polystyrene (Tosoh Corporation), molecular weight calibration method: general-purpose calibration method (polystyrene conversion), mobile phase: o-dichlorobenzene (BHT added), flow rate: 1. 0 mL / min.

In the calculation of the ratio E of the component having a peak temperature of less than 65 ° C. to the olefin resin, the differential elution curve obtained by the CFC measurement is separated into peaks by a normal distribution curve, and the ratio of the eluting component having a peak temperature of 65 ° C. or more ( wt%) was determined as E _{(> 65} ° C. ₎ and E = 100−E _{(> 65} ° C. ₎ .
The ratio (wt%) of the soluble component of orthodichlorobenzene at 50 ° C. or lower is the cumulative elution amount at 50 ° C. (including the soluble component at −20 ° C.) of the cumulative elution curve obtained by the CFC measurement.

(16) Measurement of melting point (Tm) and heat of fusion ΔH Measurement of melting point (Tm) and heat of fusion ΔH was determined by DSC under the following conditions.
Using a differential scanning calorimeter [SDC RDC220], about 10 mg of the sample was heated from 30 ° C. to 200 ° C. at a rate of 50 ° C./min in a nitrogen atmosphere, and kept at that temperature for 10 minutes. Further, the temperature was lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, kept at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature increasing rate of 10 ° C./min. The endothermic peak observed during the second heating was defined 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 and obtained.

(17) Measurement of glass transition temperature (Tg) Measurement of glass transition temperature (Tg) was obtained by performing DSC measurement under the following conditions.
Using a differential scanning calorimeter [SDC RDC220], about 10 mg of the sample was heated from 30 ° C. to 200 ° C. at a rate of 50 ° C./min in a nitrogen atmosphere, and kept at that temperature for 10 minutes. Further, the temperature was lowered to −100 ° C. at a rate of 10 ° C./min, kept at that temperature for 5 minutes, and then raised to 200 ° C. at a rate of 10 ° C./min. The glass transition temperature (Tg) is sensed in the form of the DSC curve being bent due to a change in the specific heat and the translation of the baseline during the second heating. The temperature at the intersection of the tangent to the base line at a temperature lower than the bend and the tangent to the point where the slope is maximum at the bent portion was defined as the glass transition temperature (Tg).

(18) Insoluble amount of hot xylene The sample was formed into a sheet having a thickness of 0.4 mm by a hot press (180 ° C, heating 5 minutes-cooling 1 minute), and was finely cut. About 100 mg of this was weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a closed container. Next, the screen was taken out and dried at 80 ° C. for at least 2 hours until the weight became constant. The amount of insoluble xylene (wt%) is represented by the following equation.
Thermal xylene insoluble amount (wt%) = 100 × (W3-W2) / (W1-W2)
W1: weight of screen and sample before test, W2: weight of screen, W3: weight of screen and sample after test.

(19) Intrinsic viscosity measurement Intrinsic viscosity measurement [η] was measured in decalin at 135 ° C.
Specifically, after dissolving about 20 mg of the resin in 25 ml of decalin, the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After the decalin solution was diluted by adding 5 ml of decalin, the specific viscosity ηsp was measured in the same manner as described above.
This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

(20) Ratio of Structural Unit Derived from Ethylene in Olefin Resin (C) The ratio of the constituent unit derived from ethylene in the olefin resin (C) was measured by the same method as in the above (10).

(21) Transmission Electron Microscope Observation The phase structure of the olefin resin (C) was observed using a transmission electron microscope as follows. 40 g of the olefin-based resin (C) and Irganox (40 mg), an antioxidant, were charged into Labo Plastomill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), melt-kneaded at 200 ° C. and 60 rpm for 5 minutes, and formed into a sheet by breath processing. The obtained molded body was made into a small piece of 0.5 mm square and dyed with ruthenic acid (RuO ₄ ). Further, a small piece obtained by an ultramicrotome equipped with a diamond knife was made into an ultrathin section having a thickness of about 100 nm. Carbon was vapor-deposited on this ultrathin section, and the phase structure was observed using a transmission electron microscope (H-7650, manufactured by Hitachi, Ltd.). The average particle size of the island phase was obtained as the average major axis of the island phase by performing image processing and image analysis on the obtained observation image using image analysis software “macview”.

(22) Melt flow rate (MFR)
MFR was measured by the same method as in the above (2).

(23) Viscosity η ^*
The viscosity η ^* was measured by the same method as in the above (1).

(Method for measuring physical properties of propylene-based resin composition)
(24) Haze The haze of the rectangular test piece for measuring haze obtained in each of Examples and Comparative Examples was measured using NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the haze test method specified in JIS K7136.
As the test piece, a test piece having a length of 60 mm, a width of 60 mm, and a thickness of 1 mm obtained by injection molding described below was used. The evaluation result of the haze was used as an index of transparency. That is, it was determined that those having a small value had excellent transparency.

(25) Tensile Modulus The tensile modulus of the test piece for measuring the tensile elastic modulus obtained in each of Examples and Comparative Examples was measured under the following measurement conditions in accordance with the tensile elastic modulus test method specified in JIS K7202.

<Measurement conditions>
Temperature: 23 ° C
Test piece: JIS K7162-BA dumbbell
5mm (width) × 2mm (thickness) × 75mm (length)
Tensile speed: 1.0 mm / min Distance between spans: 58 mm

(26) Low-temperature impact resistance A Charpy impact test was performed under the following conditions in accordance with JIS K7111, and a Charpy impact strength [kJ / m ² ] was determined.
<Test conditions>
Temperature: 0 ° C
Test piece: 10mm (width) x 80mm (length) x 4mm (thickness)
Single notch, edgewise vertical, notch machined

(27) Melt flow rate (MFR)
MFR was measured by the same method as in the above (2).
(Raw materials used)
(Polypropylene resin (A))
As the polypropylene resin (A), a polypropylene resin produced by a Ziegler-Natta catalyst having the following physical properties was used.
Viscosity η ^* (frequency: 25 rad / s) (210 ° C.): 550 Pa · s
MFR (230 ° C., load 2.16 kg): 26 g / 10 min Structural unit derived from propylene: 100 mol%
Mw / Mn: 5.3
mmmm (pentad fraction): 98%
Melting temperature (Tm): 160 ° C
Full width at half maximum of melting temperature (Tm) peak: 10.7 ° C

(Ethylene / α-olefin copolymer resin (B))
As the ethylene / α-olefin copolymer resin (B), Evolue SP1510 (manufactured by Prime Polymer) manufactured using a metallocene compound catalyst was used.
The ethylene / α-olefin copolymer resin (B) has the following physical properties.
Density: 913 kg / m ³
MFR (230 ° C., load 2.16 kg): 1.7 g / 10 minutes viscosity η ^* (frequency: 25 rad / s) (210 ° C.): 332 Pa · s
Constituent unit derived from ethylene: 97 mol%

(Olefin resin (C))
The olefin resin (C-1) obtained in Production Example 1 below was used as the olefin resin (C).
(Reagent used)
In the following production examples, toluene purified using an organic solvent purifier manufactured by GlassContour was used. As the toluene solution of aluminoxane, a 20% by weight methylaluminoxane / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd. was used, and triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was diluted with toluene (1.0 M).

[Production Example 1]
An olefin resin (C-1) was obtained by the following procedure.
(1) Step (P1): Production of Unsaturated Polypropylene (M-2) 500 mL of toluene and a toluene solution of methylaluminoxane (also referred to as PMAO) in a 1 L stainless steel autoclave sufficiently purged with nitrogen under a nitrogen flow. (1.5 mol / L) 0.67 mL (1.0 mmol) was added. Thereafter, the autoclave was closed and the temperature was raised to 85 ° C. Next, the propylene partial pressure was increased to 0.3 MPa while stirring the inside of the polymerization reactor at 600 rpm, and the temperature was maintained at 85 ° C. 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol / L) of dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride was introduced thereinto to initiate polymerization. The polymerization was carried out at 85 ° C. for 20 minutes while maintaining the pressure while continuously supplying propylene gas, and then 5 mL of methanol was injected to terminate the polymerization. The obtained polymerization reaction liquid was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours to obtain 14.9 g of terminally unsaturated polypropylene (M-2). Table 1 shows the analysis results of the obtained polymer.

(2) Step (P2): Production of olefin-based resin (C-1) The compound (1) represented by the following formula (1) used as a catalyst was synthesized by a known method.
15.0 g of terminally unsaturated polypropylene (M-2) and 500 ml of xylene were placed in a 1 L glass reactor sufficiently purged with nitrogen, and then heated to 110 ° C. to dissolve the macromonomer. While stirring the inside of the polymerization vessel at 600 rpm, ethylene and 1-butene were continuously supplied at 120 L / hr and 15 L / hr, respectively, to saturate the liquid phase and the gas phase. Subsequently, with ethylene and 1-butene continuously supplied, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu3Al), and toluene of the compound (1) 6.0 mL (0.012 mmol) of the solution (0.0020 mol / L), and then toluene solution (4.0 mmol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph3CB (C6F5) 4). 6.25 mL (0.025 mmol) was added, and polymerization was performed at 110 ° C. for 40 minutes under normal pressure. Termination of the polymerization was carried out by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liter 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 31.1 g of an olefin-based resin (C-1).

Table 2 shows the analysis results of the olefin-based resin (C-1).
Table 3 shows the results of analyzing the resin (C′-1) obtained by polymerization in the same manner as in Example 1 except that the terminal unsaturated polypropylene (M-1) was not added, by the method described above. This resin (C′-1) was defined as a copolymer constituting the main chain of the olefin-based resin (C-1).

  The phase structure of the obtained resin (C-1) was observed with a transmission electron microscope. As a result, the resin (C-1) had a phase separation structure composed of a sea phase formed by an amorphous component and an island phase formed by a crystalline component, and the average diameter of the island phase was 350 nm. .

[Production Example 2]
100 parts by weight of the polypropylene resin (A), 0.41 part by weight of Millad NX8000 (manufactured by Milliken) as a nucleating agent, and a phosphorus-based antioxidant [Tris (2,4-di-t-butylphenyl)] as an additive Phosphite] 0.14 parts by weight and 0.12 parts by weight of calcium stearate as a neutralizing agent are mixed by stirring with a Henschel mixer, and the mixture is mixed using a twin screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. A strand was obtained by melt-kneading under the following conditions. The obtained strand was water-cooled and then cut with a pelletizer to obtain a pellet of a raw material composition (A) in which a polypropylene resin (A) and a nucleating agent were mixed.

(Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ° C

[Example 1]
69 parts by weight of the raw material composition (A), 26 parts by weight of the ethylene / α-olefin copolymer resin (B), and 5 parts by weight of the olefin-based resin (C1) were mixed, and the mixture was mixed with Toyo Seiki Seisakusho Co., Ltd. The strand was melt-kneaded using a screw extruder (Laboplast Mill / Micro) under the following conditions to obtain a strand, and further cut with a pelletizer to obtain a pellet of a propylene-based resin composition. Table 4 summarizes the composition ratio of each component contained in the obtained propylene-based resin composition.

(Twin screw extruder conditions)
Model: Labo Plast Mill / micro screw rotation speed 45rpm
Resin temperature 200 ° C
From the obtained pellets, using an electric injection molding machine (series model EC40N II manufactured by Toshiba Machine Co., Ltd.) with a mold clamping force of 40 tons, a cylinder temperature of 190 ° C. and a mold temperature of 40 ° C., a length of 60 mm and a width of 60 mm, A 1 mm thick test piece was injection molded to obtain a square plate test piece for measuring haze.

Under the same conditions, a test piece for tensile modulus (JIS K7162-BA) and a test piece for Charpy strength (10 mm (width) × 80 mm (length) × 4 mm (thickness)) were prepared.
Using these test pieces, haze, tensile modulus, and Charpy strength (single notch, edgewise vertical, temperature 0 ° C.) were measured. The results are shown in Table 5 and FIG. FIG. 2 shows the relationship between the elastic modulus of the test piece and the Charpy strength.

[Comparative Example 1]
Without adding the olefin resin (C) so as to have the composition ratio shown in Table 4, the addition amount of the polypropylene resin (A) was 73 parts by weight, and the addition amount of the ethylene / α-olefin copolymer resin. In the same manner as in Example 1 except that the content was changed to 27 parts by weight, a pellet of the propylene-based resin composition was prepared, and a test piece was prepared from the obtained pellet, and the physical properties were measured. The results are shown in Table 5 and FIG.

[Comparative Example 2]
Pellets of a propylene-based resin composition were prepared and obtained in the same manner as in Example 1 except that the following PER was used instead of the olefin-based resin (C-1) so that the composition ratio described in Table 4 was obtained. Test pieces were prepared from the pellets, and the physical properties were measured. The results are shown in Table 5 and FIG.
PER: Propylene-ethylene copolymer Propylene-derived constituent unit content: 76 mol%
MFR (230 ° C., load 2.16 kg): 2.1 g / 10 minutes viscosity η ^* (frequency: 25 rad / s) (210 ° C.): 3250 Pa · s

[Comparative Example 3]
95 parts by weight of a propylene resin (A), 0.3 parts by weight of a nucleating agent (Mirard NX8000), 0.13 parts by weight of a phosphorus-based antioxidant [tris (2,4-di-t-butylphenyl) phosphite], Then, 0.11 part by weight of calcium stearate as a neutralizing agent was stirred and mixed with a Henschel mixer, and the mixture was melt-kneaded under the following conditions using a twin screw extruder (NR-36) manufactured by Nakatani Machine Co., Ltd. I got The obtained strand was water-cooled and then cut with a pelletizer to obtain a pellet of the raw material composition (B) in which the polypropylene resin (A) and the nucleating agent were mixed.

  To 98.24 parts by weight of the raw material composition (B), 5 parts by weight of the olefin resin (C) were mixed, and pellets of the propylene resin composition were prepared in the same manner as in Example 1; Were prepared, and the physical properties were measured. The results are shown in Table 5 and FIG.

  In general, as can be seen from the results of Comparative Examples 1 to 3 shown in FIG. 2, the rigidity (elastic modulus) tends to decrease as the low-temperature impact resistance increases. However, the propylene-based resin composition of the present invention has an excellent balance between rigidity and low-temperature impact resistance. When compared with a composition having equivalent low-temperature impact resistance, the composition of the comparative example has a high rigidity of 74 MPa. You can see that it has become. Table 5 shows that the propylene-based resin composition of the present invention is also excellent in transparency.

Claims (11)

57 to 80 parts by weight of a polypropylene resin (A) satisfying the following requirements (A1) to (A3), and 17 to 40 parts by weight of an ethylene / α-olefin copolymer resin (B) satisfying the following requirements (B1) to (B3) And 3 to 20 parts by weight of an olefin resin (C) satisfying the following requirements (C1) to (C4) (provided that the polypropylene resin (A), the ethylene / α-olefin copolymer resin (B), and the olefin resin) (A total of (C) is 100 parts by weight)) and a nucleating agent of 0.1 to 1.0 part by weight.
(A1) The viscosity η ^* (25 rad / s) of the polypropylene resin (A) measured at 210 ° C. with a rheometer is 100 to 1000 Pa · s.
(A2) The polypropylene resin (A) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 10 to 170 g / 10 minutes.
(A3) Assuming that the constituent units derived from all the monomers constituting the polypropylene resin (A) are 100 mol%, the content of the constituent units derived from propylene is more than 80 mol% and not more than 100 mol%.
(B1) The density of the ethylene / α-olefin copolymer resin (B) is 885 to 925 kg / m ³ .
(B2) The ethylene / α-olefin copolymer resin (B) has a melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C, load 2.16 kg) of 0.1 to 100 g / 10 min.
(B3) When the constitutional units derived from all the monomers constituting the ethylene / α-olefin copolymer resin (B) are 100 mol%, the composition has more than 80 mol% and 99 mol% or less of ethylene-derived constitutional units.
(C1) The olefin-based resin (C) contains a graft-type olefin-based polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of a propylene polymer. When the constitutional unit derived from all the monomers constituting the main chain of the united product [R1] is 100 mol%, the proportion of the constitutional unit derived from ethylene in the main chain is in the range of 60 to 90 mol%, and the α-olefin When the ratio of the constituent units derived from the propylene polymer is in the range of 10 to 40 mol% and the constituent units derived from all the monomers contained in the propylene polymer in the side chain is 100 mol%, the ratio of the constituent units derived from propylene is 99%. 0.5 to 100 mol%.
(C2) When the proportion of the propylene polymer contained in the olefin-based resin (C) is P% by weight, P is in the range of 30 to 60 .
(C3) The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165C, and the glass transition temperature (Tg) is in the range of -80 to -40C.
(C4) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g.   The propylene-based resin composition according to claim 1, wherein the olefin-based resin (C) has a thermal xylene insoluble amount of less than 3.0% by weight.   The olefin-based resin (C) has 20 to 80 mol% of the ethylene-derived constituent units, when the amount of the constituent units derived from all the monomers constituting the olefin-based resin (C) is 100 mol%. Propylene-based resin composition. Ratio of the component of the olefin resin (C) having a peak temperature of less than 65 ° C. in a differential elution curve measured by cross fractionation chromatography (CFC) using orthodichlorobenzene as a solvent to the olefin resin (C) The propylene-based resin composition according to any one of claims 1 to 3, wherein the value a represented by the following relational expression (Eq-1) is 1.4 or more, where E is% by weight.
a = (100−E) / P (Eq−1)   The isotactic pentad fraction (mmmm) of the propylene polymer constituting the side chain of the graft-type olefin polymer [R1] of the olefin resin (C) is 93% or more. A propylene-based resin composition according to any one of the above.   The propylene resin composition according to any one of claims 1 to 5, 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 5,000 to 100,000.   The weight average molecular weight of the ethylene / α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] is in the range of 50,000 to 200,000. The propylene-based resin composition according to the above.   The olefin-based resin (C) has a phase separation structure composed of a sea phase formed by an amorphous component and an island phase formed by a crystalline component, and the average of the island phases in a transmission electron microscope image The propylene-based resin composition according to any one of claims 1 to 7, wherein the diameter is in a range of 50 nm to 500 nm. The MFR ratio between the olefin-based resin (C) and the ethylene / α-olefin copolymer resin (B): MFR (C) / MFR (B) (230 ° C.) is 0.8 to 3.5. propylene resin composition according to any one of claims 1 to 8. The propylene-based resin composition according to any one of claims 1 to 9 , having a tensile modulus of 900 to 1400 MPa. Molded body formed from the propylene-based resin composition according to any one of claims 1 to 10.