JP5011202B2 - Propylene resin composition - Google Patents

Description

  The present invention relates to a propylene-based resin composition. More specifically, while maintaining high rigidity, the present invention has excellent mechanical property balance such as excellent impact strength and tensile rupture strength, and has improved melt fluidity and molding processing. The present invention relates to a propylene resin composition having excellent properties and molded appearance.

  Propylene-based resin compositions are used in a wide variety of molded products, including industrial parts, such as automotive parts and home appliance parts, and have excellent moldability, mechanical strength, environmental problem adaptability, and economic characteristics. It has been utilized for many purposes. In recent years, with the expansion of applications, propylene-based resin compositions are increasingly required to have better physical property balance and moldability.

Accordingly, various attempts have been made for these improvements, and attempts have been made to improve the performance of propylene-based polymers and composite methods using elastomers, inorganic fillers, and the like.
Among these, regarding the propylene polymer, a method of using a block copolymer in which a crystalline propylene polymer component and a rubber component are blended in a polymerization stage is often used.
However, this blend is generally called a propylene-based block copolymer, but is not a block copolymer in which a crystalline propylene-based polymer component and a rubber component are chemically bonded in a strict sense. Therefore, the rubber component in the crystalline propylene polymer component is coarsely phase-separated, and there is a limit as a method for improving performance such as impact properties.

Therefore, the production of a block copolymer in which a crystalline propylene polymer component and a rubber component are chemically bonded is desired as a method for controlling the phase separation structure and improving the impact resistance and tensile elongation at break. Yes.
As a method for producing such a block copolymer, a method of copolymerizing a propylene-based macromer having a copolymerizable vinyl group at its terminal with propylene or the like can be considered, but PP polymerization such as a general Zigler-Natta catalyst is possible. When the catalyst for use is used, the terminal structure becomes a saturated alkyl terminal generated mainly by chain transfer with hydrogen, and does not become a copolymerizable macromer. In addition, as a by-product unsaturated alkyl terminal, it is generated as a vinylidene terminal that cannot be copolymerized, and as a result, a block copolymer in which a crystalline propylene polymer component and a rubber component are chemically bonded is manufactured. It was impossible to do.

By the way, it is known that when a complex having a specific structure is used, a vinyl structure can be preferentially synthesized at the terminal (see, for example, Patent Document 1, Non-Patent Documents 1 and 3, etc.). And the method of synthesize | combining a propylene-type macromer using such a complex, and copolymerizing with propylene after that is disclosed (refer patent document 2, 3, nonpatent literature 2, 4, etc.).
However, although the compounds disclosed in Patent Document 2 and Non-Patent Document 4 have a branched structure, they are not composed of a crystalline propylene polymer component and a rubber component, so that mechanical properties such as impact resistance are improved. Absent. Further, the side chain molecular weight of the compound disclosed in Patent Document 2 is not sufficiently large at 13,000 Mn (about 25,000 Mw), so the effect of improving the melt properties is not sufficient. Further, the effect of reforming to improve mechanical properties is not sufficient.
In addition, since the compounds shown in Patent Document 3 and Non-Patent Document 2 use atactic polypropylene (atactic PP) as the non-crystalline site, the structure of the matrix itself composed of the crystalline propylene polymer is altered. Therefore, there is a problem that mechanical properties such as rigidity are deteriorated. Further, the molecular weight of the side chain of the compound disclosed in Patent Document 3 is at most Mn of 15,700 (Mw around 30,000), the molecular weight of the side chain is not sufficient, and the effect of improving the melt properties is not sufficient. . Further, the effect of reforming to improve mechanical properties is not sufficient.

Therefore, a propylene-based copolymer having a structure in which an amorphous polymer having a composition different from that of the crystalline propylene-based polymer as a non-crystalline site is used for the side chain is disclosed. For example, a propylene copolymer suitable as a compatibilizer for a propylene homopolymer and a propylene copolymer, specifically, a propylene copolymer having an ethylene-propylene copolymer as a side chain is disclosed. (See Patent Documents 4 and 5).
However, these propylene copolymers have an insufficient effect of improving the melt properties because the length of the branched chain is insufficient.
Furthermore, a compound obtained by copolymerizing an EPR macromer having a high molecular weight to improve the above-mentioned drawbacks and a production method are disclosed (see Patent Document 6, etc.), but the side chain molecular weight is 14900 at most (Mw 25200). However, high molecular weight is not yet sufficient, and as a result, the effect of improving melt properties is not sufficient.
Further, in these methods, slurry polymerization must be used at a relatively high temperature and low pressure in order to efficiently produce a macromer having a vinyl structure at the end, which is not preferable from the viewpoint of production efficiency and environmental load. Absent.

Moreover, in order to synthesize | combine efficiently the EPR macromer and PP macromer which have a vinyl group at the terminal, the compound which copolymerized (alpha) and (omega) -diene is disclosed (refer patent document 7, 8 etc.).
However, when α, ω-diene is used, there is a problem that the crosslinking reaction proceeds simultaneously with the copolymerization, resulting in gelation. In addition, there is a problem that unreacted α, ω-diene remains in the copolymer produced by such a method, and odor remains even in the composition or molded product.

Therefore, T.W. C. Chung et al. Have devised a polymerization method for branching isotactic PP and the structure of the resulting branched compound (see Non-Patent Document 5, etc.). In this method, a styrene derivative is used at the branch point. There is a problem in the amount of branch points and chemical stability of the branch points. Moreover, since it contains a benzene ring, there is a concern that a problem arises in the cleanliness of the polymer.
Furthermore, a technique for grafting isotactic PP to a diene portion of ethylene propylene diene methylene rubber (hereinafter referred to as EPDM) has been disclosed (see Patent Document 9, Non-Patent Document 6, etc.). The molecular weight of the non-crystalline ethylene-containing segment of about 30,000 is insufficient, and the effect of improving the melt properties is not sufficient.

On the other hand, with respect to the improvement of the physical property balance, improvement by a composite method using an elastomer or an inorganic filler has been widely attempted. Specifically, a technique of adding an inorganic filler such as talc is often used to improve the rigidity level. Furthermore, to improve the impact strength level, ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), polystyrene-ethylene / butene-polystyrene triblock copolymer (SEBS), ethylene-octene rubber (EOR), etc. A method of adding a rubber component and an elastomer is used (for example, see Patent Document 10).
In addition, a technique of adding an elastomer or an inorganic filler to a propylene polymer using a metallocene catalyst to improve the balance between rigidity and impact strength is used (for example, see Patent Document 11).

However, although these propylene-based resin compositions have achieved improvement in the physical property balance of rigidity and impact strength and improvement in molding processability to some extent, the size of the molded body, the complexity of the design, and the thinning are increasing. As it goes on, it is still not enough.
Under these circumstances, the problems in the prior art are solved, and while maintaining high rigidity, it has excellent mechanical properties such as excellent impact strength and tensile rupture strength, and improved melt flowability and molding processability. There is a need for early development of a propylene-based resin composition having an excellent molded appearance.
JP-T-2001-525461 JP-T-2001-525460 JP-T-2001-525463 JP 10-338704 A International Publication No. WO01 / 07493 International Publication No. WO02 / 079322 JP 2004-35769 A JP 2004-143434 A European Patent No. 366411 JP-A-11-29669 JP-A-10-1573 RESCONI J.H. Am. Chem. Soc 1992, 114, 1025 Shiono, T .; Macromolecules 1999, 32, 5723-5727. Macromol Rapid Commun 2000, 21, 1103 Macromol Rapid Commun 2001 2001 22,1488 Progress in polymer science 27 (2002) p70-71 Macromolecules 1991 24 561

  The object of the present invention is to provide excellent mechanical property balance such as excellent impact strength and tensile rupture strength while maintaining high rigidity in view of the above-mentioned problems of the prior art. It is in providing the propylene-type resin composition excellent in property and a molded external appearance.

  In order to solve the above problems, the present inventors have conducted various studies, and as a result, the propylene-based polymer having a specific structure (including branching) at the crystalline part and the non-crystalline part is added to the inorganic filler and the heat. As a result of blending the plastic elastomer at a specific ratio, the present propylene resin composition was found to have excellent physical property balance, and excellent performance in molding appearance such as molding processability and flow mark appearance. It came to complete.

That is, according to the first invention of the present invention, it is composed of the following component (A) that is insoluble in p-xylene at 25 ° C. and component (B) that is soluble in p-xylene at 25 ° C. i) Propylene polymer having a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000 and (ii) Degree of strain hardening (λmax) of 1.1 or more in the measurement of elongational viscosity (i) 60 to A propylene-based resin composition comprising 98% by weight, inorganic filler (ii) 1 to 39% by weight, and thermoplastic elastomer (c) 1 to 39% by weight is provided.
(A1) 20% by weight to less than 95% by weight with respect to the total amount of the polymer,
(A2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(A3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 93% or more.
(A4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(A5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (B): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (B1) to (B4).
(B1) 5% by weight to less than 80% by weight based on the total amount of the polymer,
(B2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(B3) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(B4) Contains propylene units, ethylene units and / or α-olefin units.

  According to the second invention of the present invention, in the first invention, the propylene polymer (A) has a crystalline propylene polymer segment in the side chain, and mainly comprises an amorphous propylene copolymer segment. A propylene-based resin composition having a branched structure in a chain is provided.

  Furthermore, according to the third invention of the present invention, in the first or second invention, the component (A) has a crystalline propylene polymer segment in the side chain, and the amorphous propylene copolymer segment is mainly used. A propylene-based resin composition having a branched structure in a chain is provided.

  Furthermore, according to a fourth invention of the present invention, in the first to third inventions, the component (A) contains an ethylene unit and has an ethylene content of 0.1 to 10% by weight. A propylene-based resin composition is provided.

  Furthermore, according to a fifth invention of the present invention, in the first to fourth inventions, the component (B) contains an ethylene unit, and the ethylene content is 10 wt% to less than 40 wt%. A propylene-based resin composition is provided.

  Furthermore, according to a sixth invention of the present invention, in the first to fifth inventions, there is provided a propylene-based resin composition characterized in that the thermoplastic elastomer (c) is at least one selected from ethylene-based elastomers. Provided.

As described above, the present invention relates to a propylene-based resin composition and the like, and preferred embodiments of the propylene-based polymer (A) constituting the composition include the following.
(1) The propylene polymer as described above, wherein the Q value (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) measured by GPC is 8 or less, particularly 6 or less.
(2) The propylene-based polymer described above, wherein the molecular weight M (90) at which an integral value in a curve is 90% by GPC is 2,000,000 or less.
(3) Furthermore, (iii) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min, (iv) melt tension (MT) is 10 to 100 g, (v ) The propylene-based polymer described above, wherein ME (memory effect) is 1.4 to 3.4.
(4) The intermediate component has (i) a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000, and (ii) contains a propylene unit and an ethylene unit or an α-olefin unit. The above propylene polymer.

  The propylene-based resin composition of the present invention is a novel long-chain branched propylene having a specific strain hardening degree (λmax) and isotactic triad fraction (mm fraction) that promotes improvement in the balance of physical properties and appearance of molding. Because of its main component, it has excellent mechanical properties such as excellent impact strength and tensile breaking strength, while maintaining high rigidity, and improved melt flowability for molding processability and molding appearance. And can be suitably used for injection molding, extrusion molding, injection (extrusion) foam molding, sheet molding, large blow molding and the like.

As described above, the propylene-based resin composition of the present invention contains a specific propylene-based polymer (A) (hereinafter sometimes simply referred to as “component (A)”) and an inorganic filler (B) (hereinafter referred to as “component (A)”). , And may be simply abbreviated as “component (b)”), and thermoplastic elastomer (c) (hereinafter also simply abbreviated as “component (c)”) at a specific ratio. It is characterized by that.
Hereafter, each component of the propylene-type resin composition of this invention, manufacture of a propylene-type resin composition, shaping | molding, etc. are demonstrated in detail.

[I] Constituent Component of Propylene Resin Composition I-1. Propylene polymer (a)
The propylene polymer (A) (including copolymer) used in the present invention is composed of a component (A) that is insoluble in p-xylene at 25 ° C. and a component (B) that is soluble in p-xylene at 25 ° C. (I) the weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000, and (ii) the strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more. Has properties. Hereinafter, each item will be described sequentially.

1. Weight average molecular weight (Mw) measured by GPC
The weight average molecular weight (Mw) is measured by a GPC measuring apparatus and conditions described later. In the present invention, Mw needs to be in the range of 100,000 to 1,000,000.
If this Mw is less than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, if the Mw exceeds 1 million, the melt viscosity is high, and the melt processability and moldability are lowered. . From the balance of melt processability, moldability and mechanical strength, the above range is preferable, and Mw is preferably 150,000 to 900,000, more preferably 200,000 to 800,000.
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.

Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

It is also important that there are no very high molecular weight components. Therefore, when the molecular weight distribution is measured by GPC, it is important that the molecular weight distribution does not spread to the high molecular weight side.
Accordingly, the Q value (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) measured by GPC is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.

Moreover, in order not to spread extremely to the high molecular weight side, it is preferable that the molecular weight M (90) at which the integral value in the curve is 90% by GPC is 2,000,000 or less.
Here, M (90) is a molecular weight at which the integral value in the curve is 90% by GPC measured by the GPC measuring apparatus and conditions described above, and in the present invention, M (90) is 2,000,000 or less. It is a feature. When M (90) exceeds 2,000,000, the high molecular weight component is excessively increased, and gel is generated or melt processability is deteriorated. Therefore, M (90) is 2,000,000 or less, preferably 1,500,000 or less, and more preferably 1,000,000.

2. Strain hardening degree (λmax) in measurement of elongational viscosity
The strain hardening degree (λmax) is an index representing the strength at the time of melting. When this value is large, it is considered that the melt tension is improved or the crystallization promoting action in the molding cooling process at the time of molding is increased. As a result, for example, the molding appearance can be improved during injection molding, uneven thickness is less likely to occur during blow molding, or the closed cell ratio can be increased when foam molding is performed. It is also considered that the balance of physical properties centered on rigidity can be improved.
Therefore, the strain hardening degree needs to be 1.1 or more, preferably 2.0 or more, more preferably 3.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.

  Here, regarding the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, the details of the measuring method and measuring instrument are disclosed in Polymer 42. Although there are methods described in (2001) 8663, examples of preferable measuring methods and measuring instruments include the following.

Measuring method 1:
Apparatus: Ales manufactured by Rheometrics
Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.

Measurement method 2:
Apparatus: Toyo Seiki Co., Ltd., Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: Extruded strands are prepared at a speed of 10 to 50 mm / min using an orifice with an inner diameter of 3 mm at 180 ° C. using a Capillograph manufactured by Toyo Seiki Co., Ltd.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η _E (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before the strain hardening is approximated by a straight line, the maximum value (ηmax) of the elongational viscosity η _E until the strain amount becomes 4.0 is obtained, and the approximate straight line up to that time Let the upper viscosity be ηlin.
FIG. 2 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.

The elongational viscosity and strain hardening degree calculated from the measuring method 1 and the measuring method 2 are, in principle, for measuring the inherent extensional viscosity and strain hardening degree of the substance and exhibit the same value. Therefore, either measurement method 1 or measurement method 2 may be used.
However, the measurement method 2 has a measurement restriction that a measurement sample hangs down when the molecular weight is relatively low (that is, when MFR> 2), and the measurement accuracy is lowered. In measurement method 1, when measuring a relatively high molecular weight (MFR <1), the measurement sample is deformed in a non-uniform manner, and distortion occurs at the time of measurement. There is a problem of measurement accuracy that is averaged and the strain hardening degree is estimated to be small.
Therefore, it is preferable for convenience to use the measuring method 1 for those having a low molecular weight and the measuring method 2 for those having a high molecular weight.

In general, in order to show a high degree of strain hardening, it is said that the entanglement molecular weight of polypropylene is preferably 7,000 or more as the branch length, but in order to show the above degree of strain hardening, The weight average molecular weight (Mw) measured by GPC is considered to be 15,000 or more, preferably 30,000 or more, and more preferably 50,000 or more.
As for the branched structure, in addition to the branched compound in which both the side chain and the main chain are crystalline segments, in the present invention, the branch has a crystalline segment as a side chain and an amorphous segment in the main chain. By including the compound, a high degree of strain hardening is exhibited.

3. Crystalline component (A) and non-crystalline component (B)
As described above, the propylene polymer (A) used in the present invention is composed of component (A) (hereinafter also referred to as crystalline component (A)) and component (B) (hereinafter referred to as amorphous component (B). )) And satisfy the following requirements (A1) to (A5) and (B1) to (B4), respectively.
Here, the non-crystalline component (B) is a component (CXS) that is soluble in p-xylene at 25 ° C., and the crystalline component (A) is a component that is insoluble in p-xylene at 25 ° C. ( CXIS), and separated and extracted by the following fractionation operation.

Sorting method:
A sample of 2 g was dissolved in 300 ml of p-xylene (0.5 mg / ml BHT: 2,6-di-tert-butyl-4-methylphenol included) at 130 ° C. to obtain a solution, and then at 25 ° C. Leave for 48 hours. Thereafter, it is separated into a precipitated polymer and a filtrate.
The p-xylene is evaporated from the filtrate and further dried under reduced pressure at 100 ° C. for 12 hours, and the component (CXS) dissolved in xylene at 25 ° C. is recovered. In addition, the precipitated polymer similarly removes the remaining p-xylene sufficiently, and becomes a component insoluble in xylene (CXIS) at 25 ° C.

(1) Crystalline component (A)
(I) Characteristic (A1): 20% by weight to less than 95% by weight with respect to the total of the crystalline component and the amorphous component (ie, the total amount of the polymer).
The content of the crystalline segment contributes to the mechanical properties of the entire compound. Therefore, when the content is less than 20% by weight, mechanical properties such as rigidity and heat resistance are deteriorated, and when it is more than 95% by weight, impact strength and tensile elongation at break are deteriorated. Therefore, it is preferably 30 to 90% by weight, and more preferably 40 to 85% by weight.

(II) Characteristic (A2): The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and in the present invention, Mw needs to be in the range of 100,000 to 1,000,000. If this Mw is less than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, if it exceeds 1,000,000, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably 150,000 to 900,000, more preferably 200,000 to 800,000.

(III) Characteristic (A3): The isotactic triad fraction (mm fraction) measured by ¹³ C-NMR is 93% or more.
The crystalline component (A) of the propylene-based polymer (A) used in the present invention has a stereoregularity in which the mm fraction of three propylene units obtained by ¹³ C-NMR is 93% or more. .
The mm fraction is the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control.
When the mm fraction of the crystalline component (A) is smaller than this value, the mechanical properties such as the elastic modulus of the product are lowered. Accordingly, the mm fraction is preferably 95% or more, and more preferably 96% or more.

The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg was completely dissolved in 2.5 ml of deuterated 1,1,2,2, -tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.2 ppm in the middle of the three peaks of deuterated 1,1,2,2-tetrachloroethane. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm

The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions.
Spectral assignments were made with reference to Macromolecules, (1975) 8６８, 687 and Polymer, 30: 1350 (1989).

A more specific method for determining the mm fraction will be described below.
Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit occur in three regions depending on the configuration.
mm: about 24.3 to about 21.1 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.8 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structure.

The mm fraction is calculated from the following mathematical formula (I).
mm fraction = mm area peak area / (mm area peak area + mr area peak area + rr area peak area) × 100 [%] (I)

  Moreover, the crystalline component (A) of the propylene-based polymer (A) used in the present invention can have the following partial structure containing an ethylene unit.

  The methyl group (PPE-methyl group) of the central propylene unit of the partial structure PPE resonates in the mr region around 20.9 ppm, and the methyl group (EPE-methyl group) of the central propylene unit of the partial structure EPE is 20.2 ppm. Since resonance occurs in the vicinity of the rr region, in the case of having such a partial structure, it is necessary to reduce the peak areas based on the PPE-methyl group and the EPE-methyl group from the peak areas of both the mr and rr regions. The peak area based on the PPE-methyl group can be evaluated by the peak area of the corresponding methine group (resonance at around 31.0 ppm), and the peak area based on the EPE-methyl group is resonant at the corresponding methine group (around 33.3 ppm). ) Peak area.

  Moreover, as a partial structure containing a position irregular unit, it may have the following structure (i), structure (ii), structure (iii), and structure (iv).

Among them, the carbon A, A ′, A ″ peaks appear in the mr region, and the carbon B, B ′ peaks appear in the rr region. Further, the carbon C, C ′ peaks appear in 16.8 to 17.8 ppm. .
Therefore, when calculating the mm fraction in the formula (I), the carbon appearing in the mr and rr regions from the peak area of the mr region and the peak area of the rr region, respectively, from the peak not based on the head-to-tail three-linkage. It is necessary to reduce the peak area based on A, A ′, A ″, B, B ′.

The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm), and carbon F (38.7 ppm) in the position irregular substructure [structure (i)]. It can be evaluated from 1/4 of the sum of the peak areas of resonance in the vicinity.
The peak areas based on carbon A ′ are carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J (34.1 ppm) in the position irregular substructure [structure (ii) and structure (iii)]. It can be evaluated by 2/5 of the sum of the peak areas of resonance in the vicinity and the sum of the peak areas of carbon K (resonance in the vicinity of 33.7 ppm).
The peak area based on carbon A ″ can be evaluated by the sum of the peak areas of carbon L (resonance at around 27.7 ppm).
The peak area based on carbon B can be evaluated by carbon J. The peak area based on carbon B ′ can be evaluated by carbon K.
Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
As described above, since the peak areas of mm, mr, and rr can be evaluated, it is possible to obtain the mm fraction of the three linked parts composed of the head-to-tail bond with the propylene unit as the center according to the above formula (I).

(IV) Characteristic (A4): The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
The strain hardening degree is an index representing the strength at the time of melting, and when this value is large, for example, blow molding is difficult to cause uneven thickness, and when foam molding is performed, the closed cell ratio can be increased, Further, it is considered that the crystallization promoting action in the molding cooling process at the time of the molding process can be increased, and as a result, the balance of physical properties centering on the rigidity can be improved. Therefore, this strain hardening degree needs to be 2.0 or more, preferably 3.0 or more, more preferably 4.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is generally said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
The length of the branch is preferably entangled molecular weight of 7,000 or more of polypropylene. Strictly speaking, this molecular weight is different from the weight average molecular weight (Mw) measured by GPC. Therefore, the weight average molecular weight (Mw) value measured by GPC is preferably 15,000 or more, and more preferably 30,000 or more.
As for the branched structure, in addition to the branched compound in which both the side chain and the main chain are crystalline segments, in the present invention, the branch has a crystalline segment as a side chain and an amorphous segment in the main chain By containing the compound, a high degree of strain hardening is exhibited.

(V) Characteristic (A5): Contains propylene unit and ethylene unit or α-olefin unit.
As a unit constituting the crystalline component (A), it is necessary that propylene is arranged in an isotactic manner and has crystallinity. Further, ethylene or α-olefin may be contained as a comonomer unit within the range where crystallinity is exhibited. If α, ω-diene units are present, gelation due to cross-linking is a concern, so it is necessary that no α, ω-diene units be included.
As a kind of comonomer, ethylene or a linear alpha olefin is preferable, More preferably, it is ethylene.
Regarding comonomer content, it can contain arbitrary quantity in the range which crystallinity expresses.

The melting point (Tm) measured by DSC, which is an index of crystallinity, is 120 ° C. or higher, preferably 150 ° C. or higher, more preferably 153 ° C. or higher. When the melting point (Tm) is 150 ° C. or more, it has excellent heat resistance and rigidity, and can be used for industrial parts and members. Can be used.
Moreover, the crystalline component mainly composed of such propylene units can contain a component in which an amorphous component composed of ethylene units or α-olefin units is chemically bonded in addition to propylene units. .
When ethylene is contained, the ethylene content of the crystalline component is arbitrary within the range satisfying the above, but is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight, still more preferably. Is 0.3 to 5% by weight.
The ethylene unit is measured according to the method described in Macromolecules 1982 1150 using ¹³ C-NMR.

(2) Amorphous component (B)
The propylene polymer (A) used in the present invention is characterized by having an amorphous component (B) having the following characteristics (B1) to (B4).

(I) Characteristic (B1): 5% by weight to less than 80% by weight with respect to the total of the crystalline component and the amorphous component (total amount of polymer).
The content of the amorphous component (B) in the propylene polymer (a) contributes to the mechanical properties of the entire propylene resin composition. Therefore, if the content is less than 5% by weight, mechanical properties such as impact strength and tensile strength are deteriorated. On the other hand, if the content is more than 80% by weight, rigidity and heat resistance are deteriorated. Therefore, it is preferably 10 to 70% by weight, and more preferably 15 to 60% by weight.

(II) Characteristic (B2): The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and in the present invention, Mw needs to be in the range of 100,000 to 1,000,000. When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when Mw exceeds 1,000,000, the melt viscosity is high, and the melt processability and moldability are lowered. . From the balance of melt processability, moldability and mechanical strength, it is in the above range, preferably 120,000 to 900,000, more preferably 150,000 to 800,000.

(III) Characteristic (B3): The degree of strain hardening (λmax) in the measurement of elongational viscosity is 2.0 or more.
The strain hardening degree is an index representing the strength at the time of melting, and if this value is large, for example, when blow molding, uneven thickness is difficult to occur, and the closed cell ratio can be increased when foam molding is performed, The appearance of injection molding such as the appearance of the flow mark is also improved, and the action of promoting crystallization in the molding cooling process during the molding process is increased, and as a result, the balance of physical properties centering on the rigidity can be improved. Therefore, this strain hardening degree needs to be 2.0 or more, preferably 3.0 or more, more preferably 4.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is generally said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
The length of the branch is preferably entangled molecular weight of 7,000 or more of polypropylene. Strictly speaking, this molecular weight is different from the weight average molecular weight (Mw) measured by GPC. Therefore, the weight average molecular weight (Mw) value measured by GPC is preferably 15,000 or more, and more preferably 30,000 or more.
Moreover, regarding the branched structure, in the present invention, a high degree of strain hardening is exhibited by including a branched compound having a crystalline segment as a side chain and an amorphous segment in the main chain.

(IV) Characteristic (B4): Contains propylene units, ethylene units and / or α-olefin units.
As a unit constituting the amorphous component (B), it is necessary that propylene and ethylene or α-olefin are copolymerized. Moreover, since there exists a concern about the gelatinization by bridge | crosslinking when an (alpha), (omega) -diene unit exists, it is necessary not to contain (alpha), (omega) -diene unit.
The kind of comonomer is preferably ethylene or a linear α-olefin, more preferably ethylene, in which case the ethylene content is 10 to 60% by weight, preferably 10 to 40% by weight. .
The ethylene unit is measured according to the method described in Macromolecules 1982 1150 using ¹³ C-NMR.

4). Intermediate Component The propylene polymer (A) used in the present invention preferably has the following characteristics.
That is, in the temperature rising elution fractionation with o-dichlorobenzene (hereinafter referred to as ODCB), the intermediate component eluted between 5 and 60 ° C. is present in an amount of less than 3 to 60% by weight.
This intermediate component is considered to be a component having a crystallinity intermediate between the crystalline component and the non-crystalline component, and the structure is not necessarily clear at present, but the crystalline component and the non-crystalline component are chemically separated. It is thought to contain bound components. These components with intermediate crystallinity have a role of compatibilizing the crystalline component and the non-crystalline component, and the presence of this component to some extent improves the balance between mechanical properties such as rigidity and impact strength. can do.

  Therefore, when the content of the intermediate component is less than 3% by weight, the effect of improving and improving the balance between mechanical properties such as rigidity and impact strength is reduced. On the other hand, if it exceeds 60% by weight, the rigidity and heat resistance are adversely affected. Therefore, it is preferably 4 to 50% by weight, and more preferably 5 to 40% by weight.

(1) Elevated temperature elution fractionation using ODCB (separation of intermediate and high temperature components)
The said intermediate component means the component which is insoluble in 5 degreeC ODCB and melt | dissolves in ODCB of 60 degreeC obtained using a known temperature rising column fractionation method. Moreover, a high temperature component means a component insoluble in ODCB of 101 degreeC obtained using a known temperature rising column fractionation method. The temperature rising column fractionation method is a measurement method as disclosed in, for example, Macromolecules, 21, 314 to 319 (1988).
The intermediate component and the high temperature component defined in the present invention are measured as follows. That is, a glass bead carrier (80 to 100 mesh) is packed in a cylindrical column having a diameter of 50 mm and a height of 500 mm, and maintained at 140 ° C.
Next, 200 mL of a sample ODCB solution (10 mg / mL) dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 5 ° C. at a rate of temperature decrease of 10 ° C./hour. Hold at 5 ° C. for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at 5 ° C., 800 mL of ODCB at 5 ° C. is allowed to flow at a flow rate of 20 mL / min to elute and remove components dissolved in ODCB at 5 ° C. existing in the column.
Next, the column temperature was raised to 60 ° C. at a temperature rising rate of 10 ° C./min, and left at 60 ° C. for 1 hour, and then 800 mL of a 60 ° C. solvent (ODCB) was flowed at a flow rate of 20 mL / min to 5 ° C. The components insoluble in ODCB and soluble in ODCB at 60 ° C. are eluted and collected.
The ODCB solution containing a component insoluble in ODCB at 5 ° C. and soluble in ODCB at 60 ° C. is concentrated to 20 mL using an evaporator, and then precipitated in 5 volumes of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer. This is the “intermediate component” in the present invention.
Next, the column temperature was raised to 101 ° C. at a temperature rising rate of 10 ° C./min, and left at 101 ° C. for 1 hour, and then the solvent (ODCB) at 101 ° C. was allowed to flow at 800 mL at a flow rate of 20 mL / min. A component insoluble in ODCB and soluble in ODCB at 101 ° C. is eluted.
Subsequently, the column temperature was raised to 140 ° C. at a temperature rising rate of 10 ° C./min, and left at 140 ° C. for 1 hour, and then 800 mL of a 140 ° C. solvent (ODCB) was flowed at a flow rate of 20 mL / min to give 101 ° C. The components insoluble in ODCB are eluted.
The ODCB solution containing components insoluble in ODCB at 101 ° C. is concentrated to 20 mL using an evaporator, and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer. This is the “high temperature component” in the present invention.

(2) Characteristics of Intermediate Component The weight average molecular weight (Mw) measured by GPC of this intermediate component needs to be 100,000 to 1,000,000. If this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, if it exceeds 1,000,000, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably 120,000 to 900,000, more preferably 150,000 to 800,000.
Furthermore, this component can contain propylene units and ethylene or alpha olefin units. When an ethylene unit is included, the ethylene content is preferably 7 to 25% by weight.

(3) Characteristics of high-temperature component The high-temperature component is a fraction from which a highly crystalline component is eluted, and this fraction can contain a propylene unit and an ethylene unit or an α-olefin unit. When an ethylene unit is included, the ethylene content is preferably 0.1 to 10% by weight. In this case, ethylene contained in the non-crystalline fragment chemically bonded to the crystalline segment is detected as the ethylene unit to be detected. In this case, ethylene is randomly distributed with respect to propylene. There is a general method of using r1 × r2 using a copolymerization ratio as an index representing randomness. In this case, it is preferable that this numerical value is 2 or less.

5. Production Method of Propylene Polymer (A) The method for producing the propylene polymer (A) used in the present invention is (i) the weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000. (Ii) In addition to the degree of strain hardening (λmax) in the measurement of elongational viscosity being 1.1 or more, the crystalline components (A) and (B1) to (B4) of (A1) to (A5) ) Of the non-crystalline component (B) is sufficient as long as it is a method for obtaining a propylene-based polymer, and there is no particular limitation. (I) propylene alone, or propylene and ethylene or α-olefin are polymerized, and ethylene or α-olefin is polymerized in an amount of 0 to 10% by weight based on the total monomer components. First step and And (ii) a second step of polymerizing propylene and ethylene or α-olefin, and polymerizing ethylene or α-olefin with respect to all monomer components in an amount of 10 to 90% by weight. The coalescence can be produced with high productivity.

(1) Catalyst component (a):
The catalyst component (a) used in the present invention is a metallocene compound having hafnium as a central metal represented by the following general formula (1).

[In General Formula (1), each of R ¹¹ and R ¹² independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or silicon containing 1 to 6 carbon atoms. Represents an alkyl group, an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, a nitrogen or oxygen having 4 to 16 carbon atoms, and a heterocyclic group containing sulfur, and at least one of R ¹¹ and R ¹² One shows a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. Each of R ¹³ and R ¹⁴ is independently an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, or 6 to 16 carbon atoms. An aryl group of 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, a silicon-containing aryl group having 6 to 16 carbon atoms, a nitrogen or oxygen having 6 to 16 carbon atoms, and a heterocyclic group containing sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group, an oligosilylene group, or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted group. 2-furfuryl group, more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.

R ¹³ and R ¹⁴ are preferably an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, or a silicon-containing aryl group having 6 to 16 carbon atoms. In the range of 6 to 16, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogen-containing carbon atoms having 1 to 6 carbon atoms on the aryl cyclic skeleton You may have a hydrogen group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-tbutylphenyl group, a 2,3-dimethylphenyl group, a 3,5-ditbutylphenyl group, a 4-phenyl-phenyl group, or a chlorophenyl. Group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group, a 4-tbutylphenyl group, and a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In General Formula (1), X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. ˜20 silicon-containing hydrocarbon group, C 1-20 oxygen-containing hydrocarbon group, amino group, or C 1-20 nitrogen-containing hydrocarbon group. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and s-butyl, vinyl, propenyl, Examples include alkenyl groups such as cyclohexenyl, arylalkyl groups such as benzyl, arylalkenyl groups such as trans-styryl, and aryl groups such as phenyl, tolyl, 1-naphthyl, and 2-naphthyl.
Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, allyloxy groups such as phenoxy and naphthoxy, arylalkoxy groups such as phenylmethoxy, and furyl groups. And oxygen-containing heterocyclic groups.
Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino, arylamino groups such as phenylamino and diphenylamino, (methyl) ( (Alkyl) (aryl) amino groups such as phenyl) amino, and nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl.

In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, and trichloromethyl groups.
Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dialkyl such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl. (Alkyl) (aryl) silylmethyl group and the like can be mentioned.

In the general formula (1), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms silylene A group, an oligosilylene group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-i [Denyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl) -2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1 '-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1, '-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- ( 9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -i Denyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium Dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-di Methylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl) 2-Furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl} ] Hafnium, etc.

Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (2-Naphtyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium.
Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium , Etc.

(2) Catalyst component (b):
Next, the catalyst component (b) used in the present invention is an ion-exchange layered silicate.
(I) Types of ion-exchange layered silicates In the present invention, ion-exchange layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces in which ionic bonds or the like are formed by a binding force. It refers to a silicate compound that has a crystal structure that is stacked in parallel and that allows the contained ions to be exchanged. Most silicates are naturally produced mainly as the main component of clay minerals, and are generally dispersed / swelled in water and purified by differences in sedimentation rate, etc., but they can be completely removed. Although it may be difficult and contains impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicate, they may be included. Depending on the type, amount, particle diameter, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (b).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product.

In addition, in the present invention, if there is ion exchange properties before chemical treatment, the physical and chemical properties are changed by the treatment, and silicates having no ion exchange properties or layer structures are also included. Treated as an ion-exchanged layered silicate.
Specific examples of the ion-exchange layered silicate include, for example, layered silicates having a 1: 1 type structure or a 2: 1 type structure described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1988) and the like. Can be mentioned.
The 1: 1 type structure is based on the stacking of the 1: 1 layer structure in which one layer of tetrahedron sheet and one layer of octahedron sheet are combined as described in the above “clay mineralogy” and the like. The 2: 1 type structure is a structure based on a stack of 2: 1 layer structures in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.

  Specific examples of ion-exchangeable layered silicates in which the 1: 1 layer is the main constituent layer include kaolin silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite, chrysotile, risardite, antigolite, etc. Examples include serpentine silicates.

  Specific examples of ion-exchangeable layered silicates with 2: 1 layers as main constituent layers include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and vermiculite groups such as vermiculite. Examples thereof include mica group silicates such as silicate, mica, illite, sericite, and sea green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, and the like. These may form a mixed layer.

  Among these, the main component is preferably an ion-exchange layered silicate having a 2: 1 type structure. More preferably, the main component is a smectite group silicate, and still more preferably, the main component is montmorillonite.

  The type of interlayer cations (cations contained between the layers of the ion-exchange layered silicate) is not particularly limited, but as a main component, alkali metals of the first group of the periodic table such as lithium and sodium, calcium and magnesium Alkali earth metals of Group 2 of the periodic table, etc., or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, gold, etc. are relatively It is preferable in that it can be easily obtained.

(II) Granulation of ion-exchangeable layered silicate The ion-exchangeable layered silicate may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the granulated ion-exchange layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchange layered silicate is used as a catalyst component.

  Processing of the shape of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the chemical treatment (that is, the following chemical treatment is performed on the ion-exchange layered silicate that has been processed in advance). The shape may be processed after chemical treatment.

  Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferably, agitation granulation method, spray granulation method, rolling granulation method, and fluidized granulation method are exemplified, and particularly preferably, agitation granulation method and spray granulation method are exemplified.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the catalyst component (b) in the raw material slurry for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. is there. The inlet temperature of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.

  In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a method using forced stirring using polytron or the like, a method using dyno mill, pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.

  The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

(III) Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of the catalyst component (b) according to the present invention can be used as it is without any treatment, but it is desirable to perform the chemical treatment. The chemical treatment of the ion-exchange layered silicate refers to bringing an acid, salt, alkali, organic substance or the like into contact with the ion-exchange layered silicate.

  A common effect of chemical treatment is to exchange interlayer cations. In addition, various chemical treatments have the following various effects. For example, according to the acid treatment with acids, impurities on the silicate surface can be removed and the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. This contributes to increasing the acid strength of the silicate and increasing the amount of acid sites per unit weight.

  In alkali treatment with alkalis, the crystal structure of the clay mineral is destroyed, resulting in a change in the structure of the clay mineral.

  Below, the specific example of a processing agent is shown. In the present invention, a combination of the following acids and salts may be used as the treating agent. Moreover, the combination of these acids and salts may be sufficient.

(I) Acids In addition to removing impurities on the surface or exchanging cations existing between layers, the acid treatment is carried out in part or all of cations such as Al, Fe and Mg incorporated in the crystal structure. Can be eluted. Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.

(Ii) Salts Salts are composed of a cation selected from the group consisting of an organic cation, an inorganic cation, and a metal ion, and an anion selected from the group consisting of an organic anion, an inorganic anion, and a halide ion. Examples of such salts are exemplified. For example, at least one selected from the group consisting of a cation containing at least one atom selected from Groups 1 to 14 of the periodic table, a halogen anion, an inorganic Bronsted acid, and an organic Bronsted acid anion. A preferred example is a compound composed of an anion.

Specific examples of such salts include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), LiNO ₃ , Li (OOCCH ₃ ), NaCl, NaBr, Na ₂ SO ₄ , and Na ₃ (PO ₄ ). , NaNO ₃ , Na (OOCCH ₃ ), KCl, KBr, K ₂ SO ₄ , K ₃ (PO ₄ ), KNO ₃ , K (OOCCH ₃ ), CaCl ₂ , CaSO ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , Ti (OOCCH ₃ ) ₄ , MgCl ₂ , MgSO ₄ , Mg (NO ₃ ) ₂ , Mg ₃ (C ₆ H ₅ O ₇ ) ₂ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl _{4 and the} like.

Also, Cr (OOCH ₃ ) ₂ OH, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₃ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , MnBr ₃ FeI ₃ , FeC ₆ H ₅ O ₇ , Co (OOCH ₃ ) _{2 and the} like.

Furthermore, CuCl ₂ , CuBr ₂ , Cu (NO ₃ ) ₂ , CuC ₂ O ₄ , Cu (ClO ₄ ) ₂ , CuSO ₄ , Cu (OOCCH ₃ ) ₂ , Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO _{4 and the} like.
Among these, a compound in which the anion is composed of an inorganic Bronsted acid or a halogen and the cation is composed of Li, Mg, or Zn is preferable.
Particularly preferred compounds in such salts include LiCl, Li ₂ SO ₄ , MgCl ₂ , MgSO ₄ , ZnCl ₂ , ZnSO ₄ , Zn (NO ₃ ) ₂ , Zn ₃ (PO ₄ ) ₂ .

(Iii) Other treatment agents In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treatment agent in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

  Examples of organic treating agents include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5- Examples thereof include, but are not limited to, pentamethylanilinium, N, N-dimethyloctadecylammonium, and octadodecylammonium.

  Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.

(Iv) Chemical treatment conditions The various treatment agents described above may be dissolved in an appropriate solvent and used as a treatment solution, or the treatment agent itself may be used as a solvent. Although there is no restriction | limiting in particular as a solvent which can be used, Water and alcohol are common, and water is especially preferable. For example, when performing acid treatment as a chemical treatment, by controlling acid treatment conditions such as acid treatment agent concentration, ratio of ion-exchangeable layered silicate and treatment agent, treatment time, treatment temperature, etc., an ion layered silicate compound Can be controlled by changing to a predetermined composition and structure.

Regarding such an acid treating agent concentration, it is preferable to treat with an acid having an acid concentration (N) satisfying the following formula.
N ≧ 1.0
The acid concentration N shown here is defined as the number of moles of acid × the valence of acid / the volume of the acid aqueous solution (unit: mole / liter). However, when a salt is allowed to coexist, the amount of water of crystallization contained in the salt compound is considered, but the volume change due to the salt is not considered. As for the specific gravity of the acid aqueous solution, the basic edition IIp6 (edited by the Chemical Society of Japan, published by Maruzen, revised 3rd edition) of the Chemical Handbook was cited. The upper limit of the acid concentration N is preferably 20 or less, particularly 15 or less, from the viewpoint of safety in handling, ease, and equipment.

The ratio of the ion-exchange layered silicate to the treatment agent is not particularly limited, but preferably, the ion-exchange layered silicate [g]: treatment agent [acid valence × mol number] = 1: 0.001. ˜1: About 0.1.
The acid treatment temperature is preferably in the range of room temperature to the boiling point of the treatment agent solution, the treatment time is selected from 5 minutes to 24 hours, and at least a part of the material constituting the ion-exchange layered silicate is It is preferable to carry out under the conditions for removal or replacement. The acid treatment conditions are not particularly limited, but when sulfuric acid is used as the chemical treatment, the treatment temperature is from 80 ° C. to the boiling point of the treating agent solvent and the treatment time may be from 0.5 hours to less than 5 hours. preferable.

(IV) Drying of ion-exchange layered silicate It is possible to remove the excessive treatment agent and ions eluted by the treatment after the chemical treatment is performed, which is preferable. At this time, generally, a liquid such as water or an organic solvent is used. After the dehydration, drying is performed. In general, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C. Exceeding 800 ° C. is not preferable because it may cause structural destruction of the silicate.

  Since these ion-exchange layered silicates have different characteristics depending on the drying temperature even if they are not structurally destroyed, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

(V) Composition after chemical treatment of ion-exchangeable layered silicate The chemical-treated ion-exchangeable layered silicate is 0.01% as the atomic ratio of Al / Si as the catalyst component (b) according to the present invention. It is preferably -0.25, preferably 0.03-0.24, more preferably 0.05-0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion. In addition, as a method for controlling the Al / Si atomic ratio within the above range, there is a method in which montmorillonite is used as the ion-exchange layered silicate before chemical treatment and the chemical treatment described in (III) is performed. .
Aluminum and silicon in the ion-exchange layered silicate are measured by a method of preparing a calibration curve by a chemical analysis method by JIS method and quantifying with a fluorescent X-ray.

(3) Catalyst component (c):
The catalyst component (c) used in the present invention is an organoaluminum compound, and preferably an organoaluminum compound represented by the general formula (AlR _n X _3-n ) _m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Catalyst adjustment:
The catalyst for olefin polymerization according to the present invention contains the catalyst components (a), (b) and (c). These may be contacted in the polymerization tank or outside the polymerization tank and preliminarily polymerized in the presence of olefin.
The olefin refers to a hydrocarbon having at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. An olefin having 3 or more carbon atoms is preferable.

  The amount of the catalyst components (a), (b) and (c) used is arbitrary, but the ratio of the transition metal in the catalyst component (b) to the aluminum in the catalyst component (c) is the catalyst component ( a) It is preferable to contact so that it may become 0.1-1000 (micromol): 0-100,000 (micromol) per 1g. In addition to the catalyst component (a), other types of complexes may be used as long as the substance of the present invention can be produced.

In this case, it is preferable to combine a metallocene compound capable of copolymerizing the terminal vinyl macromer produced by the catalyst component (a) and producing a high molecular weight polymer compared to the catalyst component (a). By combining with a compound, a polymer having improved melt properties and mechanical properties which are requirements of the present invention can be obtained.
Examples of such a metallocene compound include a catalyst component (a-2) represented by the following general formula (2).

The compound represented by the general formula (2) is a metallocene compound, and in the general formula (2), Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a carbon number. A divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group It is. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.
Me is zirconium or hafnium, preferably hafnium.
Furthermore, X ²¹ and Y ²¹ are auxiliary ligands, and react with the cocatalyst of component [b] to generate an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ²¹ and Y ²¹ are not limited to the type of ligand, and each independently represents hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In general formula (2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. is there. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ²³ and R ²⁴ each independently contains a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, or a plurality of hetero elements selected from these. A good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluorobiphenylyl), 4- (2-chlorobiphenylyl), 1-naphthyl, 2-naphthyl, 3,5-dimethyl-4-tert-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl Etc.

Non-limiting examples of the metallocene compound include the following.
For example, dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazulenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl) ) -4-Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl }] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl -4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2 -Methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, and the like.

  When using other types of catalyst component (a-2), the ratio of the amount of catalyst component (a-2) to the total amount of catalyst component (a) and catalyst component (a-2) is propylene-based. Although it is arbitrary as long as the characteristics of the polymer are satisfied, it is preferably 0.01 to 0.6. By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity, and particularly preferably for the production of propylene-based polymers for applications that require higher melt properties and high catalyst activity, It is 0.03-0.4, More preferably, it is the range of 0.07-0.2.

  The order in which the catalyst component (a), the catalyst component (b), and the catalyst component (c) are brought into contact is arbitrary, and after contacting two of these components, the remaining one component may be brought into contact. Three components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of the aliphatic saturated hydrocarbon and the aromatic hydrocarbon include hexane, heptane, toluene and the like. Further, as a prepolymerized monomer, propylene can be used as a solvent.

[Prepolymerization]:
As described above, the catalyst according to the present invention is preferably subjected to a prepolymerization process comprising a small amount of polymerization by bringing an olefin into contact therewith. The olefin used is not particularly limited, but as described above, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkanes and styrene. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The prepolymerization amount is preferably 0.01 to 100, more preferably 0.1 to 50, by weight ratio of the prepolymerized polymer to the catalyst component (b). Moreover, a catalyst component (c) can also be added or added at the time of prepolymerization.
A method of coexisting a polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or titania at the time of contacting or after the contact of the above components is also possible.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include reduced-pressure drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. May be. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

[Detailed description of polymerization method]:
As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst comprising the catalyst component (a), the catalyst component (b) and the catalyst component (c) and the monomer come into efficient contact. Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
Further, the number of polymerization stages is not particularly limited as long as the substance of the present invention can be produced. However, it is possible to employ a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, and two stages of gas phase polymerization, and more. It is possible to produce with the number of polymerization stages.
However, to produce the materials disclosed in the present invention, a crystalline propylene macromer with a high vinyl end is produced in the first step and copolymerized with propylene and ethylene or alpha olefin in the second step. Preferably, by doing so, the macromer produced in the first step is copolymerized in the second step, so that the graft copolymer has a crystalline segment in the side chain and an amorphous segment in the main chain. The polymer of this invention containing this can be manufactured.
In order to obtain the compound disclosed in the present invention, the first step is performed by bulk polymerization and the second step is performed by gas phase polymerization, or both the first step and the second step are performed by gas phase polymerization. Is preferred. The reason for this is that the environmental load due to the fact that no solvent is substantially used can be reduced, and the manufacturing process can be simplified.

[First step]:
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene or the like is used alone or as a mixture as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably from 0 to 3 MPaG, preferably from 0 to 2 MPaG.
In the case of the bulk polymerization method, the polymerization temperature is 0 to 80 ° C, preferably 60 to 80 ° C, more preferably 65 to 75 ° C. The polymerization pressure is 0 to 5 MPaG, preferably 0 to 4 MPaG.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Moreover, it is preferable not to use hydrogen as a molecular weight modifier in order to suppress chain transfer due to hydrogen and increase the terminal vinyl content.

[Second step]:
In the case of gas phase polymerization, the polymerization temperature is 20 to 90 ° C, preferably 30 to 80 ° C, and more preferably 50 to 80 ° C. In addition, hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Here, the propylene-ethylene (or α-olefin) copolymer to be produced is partially copolymerized with a low vinyl terminal content, and both the main chain and the side chain are (non-crystalline) propylene-ethylene random copolymer. It is thought that a polymer having a branched structure having a segment is formed. In this case, the lower the ethylene content in the amorphous propylene-ethylene random copolymer, the higher the vinyl terminal content. That is, by reducing the ethylene content in the amorphous propylene-ethylene random copolymer, it is possible to increase λmax of the CXS component of the propylene-based polymer (a) of the present invention. Therefore, in order to make λmax of the CXS component within a preferable range, the ethylene content is preferably 10% by weight to less than 40% by weight. It is necessary to control the ethylene gas composition in the gas phase to 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more. The upper limit is 65 mol% or less, preferably 60 mol% or less, and more preferably 50 mol% or less.

The propylene-based polymer (I) used in the present invention thus obtained has (i) a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000, and (ii) strain in measurement of elongational viscosity. The degree of cure (λmax) is 1.1 or more, which means that it contains a branched polymer.
Such a branched polymer is a copolymer in which a crystalline segment is grafted to an amorphous segment as a side chain. In particular, such a graft copolymer is present in the CXIS component (A) or the CXIS component (A) and the CXS component (B). As such a graft copolymer, it has a crystalline segment in the side chain, and the non-crystalline segment becomes the main chain. The macromer of the crystalline component is produced in the first stage, and the amorphous polymer is produced in the second stage. Naturally, from the viewpoint of the polymerization mechanism of being copolymerized with the active ingredient.

The propylene polymer (A) used in the present invention thus obtained has (iii) MFR (test conditions: 230 ° C., 2.16 kg load) of 0.1 to 300 g / 10 min. iv) It is desirable that the melt tension (MT) is 10 to 100 g, and (v) ME (memory effect) is 1.4 to 3.4.
When MFR is less than 0.1 g / 10 min, fluidity and molding processability are lowered, and rigidity is also lowered. On the other hand, when the MFR exceeds 300 g / 10 min, melt processability and impact strength are lowered. Moreover, within this range, it is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 80 g / 10 minutes, and particularly preferably 3 to 40 g / 10 minutes.
On the other hand, if the melt tension (MT) is less than 10 g, the melt tension becomes insufficient and the moldability becomes poor, and if MT exceeds 100 g, the spreadability becomes worse and the moldability becomes worse. More preferably, it is 10-50g in the range of MT.
Furthermore, if the ME (memory effect) is less than 1.4, a flow mark is generated at the time of injection molding, resulting in poor appearance. On the other hand, if the ME exceeds 3.4, welds are likely to occur, resulting in poor appearance. Absent. More preferably, it is 1.5-2.4.

6). Blending Ratio The blending ratio of the propylene polymer (A) in the propylene resin composition of the present invention is 60 to 98% by weight, preferably 60 to 94% by weight, particularly preferably 60 to 90% by weight. When the blending ratio of the component (C) is less than 60% by weight, the impact strength of the propylene-based resin composition decreases, and when it exceeds 98% by weight, the rigidity decreases.
In addition, as long as it is in the range of the above-mentioned characteristic, 2 or more types of propylene-type polymers (I) may be used together.

I-2. Inorganic filler (b)
The inorganic filler (b) used in the present invention is talc, wollastonite, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, barium sulfate, mica, glass fiber, glass balloon, basic magnesium sulfate whisker, titanium Examples include potassium acid whisker, aluminum borate whisker, carbon fiber, clay, organic clay, aluminum hydroxide, magnesium hydroxide, magnesium oxide, and zinc oxide. It is used for the purpose of improving the balance of physical properties centered on the material and developing dimensional characteristics. These inorganic fillers may be surface-treated, or may be used in combination of two or more.

Of these, talc is preferable, and talc is effective in improving rigidity, dimensional stability of the molded body, adjustment thereof, and the like. The talc preferably has an average particle size of 1.5 μm to 15 μm, particularly preferably 2 to 8 μm. If the average particle size of talc is less than 1.5 μm, it aggregates and the appearance of the molded product is lowered, and if it exceeds 15 μm, the impact strength is lowered, which is not preferable.
The talc is produced, for example, by pulverizing raw talc with an impact pulverizer or a micron mill type pulverizer, or further pulverizing with a jet mill or the like and then adjusting the classification with a cyclone or micron separator. .

The talc may be chemically or physically surface-treated with various metal soaps or surfactants, and so-called compressed talc having an apparent specific volume of 2.50 ml / g or less may be used. The average particle diameter of the talc is a value measured using a laser diffraction / scattering particle size distribution meter, and examples of the measuring apparatus include Horiba LA-920 type.
The talc has an average aspect ratio of 4 or more, more preferably 5 or more. Measurement of the aspect ratio of the talc is obtained from a value measured with a microscope or the like.

  The blending ratio of the inorganic filler (b) used in the present invention is 1 to 39% by weight, preferably 3 to 35% by weight, and particularly preferably 5 to 30% by weight. When the blending ratio of the inorganic filler (b) is less than 1% by weight, the propylene-based resin composition has insufficient rigidity, and when it exceeds 39% by weight, impact strength and molded appearance are deteriorated.

I-3. Thermoplastic elastomer (C)
The thermoplastic elastomer (c) used in the present invention is an ethylene / α-olefin-based elastomer or a styrene-based elastomer, which improves the physical property balance centered on the impact strength of the propylene-based resin composition and is good. Used for the purpose of exhibiting moldability, dimensional characteristics and the like.
Of the ethylene / α-olefin-based elastomers or styrene-based elastomers, it is preferable to use ethylene / α-olefin-based elastomers in terms of moldability and economy.

Here, the ethylene / α-olefin-based elastomer is a rubber-like random copolymer of ethylene and α-olefin, and is usually also referred to as ethylene-based rubber, and is itself supplied in the form of pellets or crumbs. Examples include Mitsui Chemicals' Toughmer, EBM, and Dow Chemical Japan's Engage.
As this ethylene / α-olefin-based elastomer, it is preferable to use one having an elution component as measured by a CFC analyzer of 98% by weight or more at 40 ° C. or less.
Examples of the α-olefin to be copolymerized include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and the like. Of these, 1-butene, 1-hexene and 1-octene are preferable.
The content of α-olefin in the ethylene / α-olefin elastomer is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the density is preferably 0.80 to 0.90 g / cm ^3. More preferably, it is 0.86-0.88 g / cm < ³ >.

The styrene elastomer is a block or random copolymer of styrene and ethylene, propylene, 1-butene, butadiene, isoprene or the like, or a hydrogenated product thereof. The amount of bound styrene in the styrene elastomer is preferably 5 ˜45 wt%, more preferably 10 to 40 wt%, and the density is preferably 0.88 to 0.95 g / cm ³ , more preferably 0.89 to 0.92 g / cm ³ . is there.

  The production of the ethylene / α-olefin elastomer can be obtained by polymerization using a known titanium catalyst or metallocene catalyst. In the case of a styrene-based elastomer, it can be obtained by a usual anionic polymerization method and its polymer hydrogenation technique.

The MFR (230 ° C., 2.16 kg load) of these elastomers needs to be 0.1 g / 10 min or more, preferably 0.1 to 80 g / 10 min, particularly preferably 1 to 30 g / 10 min. is there. When the MFR is less than 0.1 g / 10 min, the moldability, the molding appearance and the paintability of the propylene-based resin composition become inferior.
Two or more of these elastomers may be used in combination.

  The blending ratio of the thermoplastic elastomer (c) used in the present invention is 1 to 39% by weight, preferably 3 to 35% by weight, and particularly preferably 5 to 30% by weight. When the blending ratio of the thermoplastic elastomer (c) is less than 1% by weight, the impact strength of the propylene-based resin composition is insufficient, and when it exceeds 39% by weight, rigidity, heat resistance, molded appearance, and economical efficiency are obtained. descend.

I-4. Other ingredients (d)
In the propylene-based resin composition of the present invention, in addition to the above components (a), (b), and (c), for example, the effects of the present invention can be further improved within a range that does not significantly impair the effects of the present invention. Or other components (d) can be blended to impart other effects.
Specifically, antistatic agents such as nonionics, light stabilizers such as hindered amines, UV absorbers such as benzotriazoles, nucleating agents such as sorbitols, foaming agents such as physical foaming agents, organometallic salts Dispersants such as pigments, colorants such as pigments, antioxidants such as phenols, neutralizers such as inorganic compounds, lubricants such as fatty acid amides, metal deactivators such as nitrogen compounds, nonionic interfaces, etc. Activators, antibacterial and antifungal agents such as thiazoles, flame retardants such as halogen compounds, fluorescent brighteners, anti-foaming agents, cross-linking agents, peroxides, process oils (blending oils), anti-blocking agents , Plasticizers, polyolefins other than the above components (a) to (c), thermoplastic resins such as polyamide and polyester, inorganic (organic) fillers, elastomers (rubbers), and the like. . These components may be added to the composition, may be added to each component, or two or more of these components may be used in combination.

  As the antistatic agent, for example, a nonionic or cationic antistatic agent is effective for imparting and improving the antistatic properties of the propylene-based resin composition and the molded body thereof. Specific examples include polyoxyethylene alkylamines; polyoxyethylene alkylamides; polyoxyethylene alkylphenyl ethers; stearic acid monoglycerides; alkyldiethanolamines; alkyldiethanolamides; alkyldiethanolamine fatty acid monoesters;

  For example, hindered amine compounds, benzotriazoles, benzophenones, and salicylates as light stabilizers and ultraviolet absorbers are effective for imparting and improving the weather resistance and durability of the propylene resin composition and molded articles thereof. Specific examples of the hindered amine compound include a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine; poly [[6- (1, 1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebake Bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and the like, and examples of the benzotriazole type include 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole; 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole and the like. -Methoxybenzophenone; 2-hydroxy-4-n-octoxybenzophenone and the like. Examples of salicylates include 4-t-butylphenyl salicylate; 2,4-di-t-butylphenyl 3 ', 5'-di -T-butyl-4'-hydroxybenzoate and the like.

  As a nucleating agent, for example, inorganic, sorbitol, carboxylic acid metal salt and organic phosphate are effective for imparting and improving the rigidity, heat resistance, hardness, etc. of the propylene resin composition and its molded product. It is. Specific examples include talc as an inorganic type; silica and the like, and 1,3,2,4-dibenzylidene-sorbitol as a sorbitol type; 1,3,2,4-di- (p-methyl-benzylidene). Sorbitol; 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol; 1,3,2,4-di- (2 ′, 4′-di-methyl-benzylidene) sorbitol; p-chlorobenzylidene-2,4-p-methyl-benzylidene-sorbitol; 1,3,2,4-di- (p-propylbenzylidene) sorbitol and the like. Hydroxy-di-pt-butylbenzoate; sodium benzoate; calcium montanate and the like. 4-t-butylphenyl) phosphate; sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate; lithium-2,2′-methylene-bis (4,6- And di-t-butylphenyl) phosphate.

  As the foaming agent, for example, a physical foaming agent and a chemical foaming agent are effective for reducing the weight of the propylene-based resin composition and its molded product, and for imparting and improving rigidity and dimensional characteristics. Specific examples of the physical blowing agent include carbon dioxide gas; nitrogen gas; air; propane; butane; dichlorodifluoromethane, and the like. Examples of the chemical blowing agent include citric acid; Hydrazide; N, N′-dimethyl-N, N′-dinitrosotephthalamide; P-toluenesulfonyl semicarbazide and the like.

  As a dispersant, for example, an organic metal salt or the like enhances dispersibility of inorganic fillers and coloring pigments, and imparts rigidity, heat resistance, weld appearance, flow mark appearance, texture, etc. of the propylene-based resin composition and its molded body, It is effective for improvement. Specific examples include calcium stearate; magnesium stearate; calcium behenate; magnesium behenate; zinc behenate; zinc montanate; calcium montanate;

  As a colorant, for example, inorganic or organic pigments are effective for imparting or improving the colored appearance, appearance, texture, commercial value, weather resistance, durability, etc. of the propylene resin composition and its molded product. It is. Specific examples of inorganic pigments include titanium oxide; iron oxide (eg, bengara); chromic acid (eg, galvanized lead); molybdic acid; selenide sulfide; ferrocyanide and carbon black. Insoluble azo chelates; insoluble azo chelates; condensable azo chelates; other azo chelates such as azo chelates; phthalocyanine blue; phthalocyanine pigments such as phthalocyanine green; anthraquinones; perinones; perylene; Dye lake; quinacridone type; dioxazine type; isoindolinone type. Moreover, in order to make a metallic tone or a pearl tone, an aluminum flake; a pearl pigment can be contained. Moreover, dye can also be contained.

[II] Production and molding of propylene-based resin composition The propylene-based resin composition of the present invention comprises the above component (A), component (B), component (C), and, if necessary, other components (D), It mixes with the said mixing | blending ratio, and manufactures by kneading and granulating using normal kneading machines, such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader.
In this case, it is desirable to select a kneading / granulating method capable of improving the dispersion of each component, and usually kneading / granulating using a twin screw extruder. In this kneading and granulation, the above component (a), component (b), component (c), and other components (d) may be kneaded at the same time, if necessary, and the performance is improved. For example, the components (a) and (b) may be partly or entirely kneaded, and then the remaining components may be kneaded and granulated.

The propylene-based resin composition is molded by injection molding (including gas injection molding) or injection compression molding (including press injection, hot flow stamping molding, gas injection compression molding) to obtain those molded bodies. I can do it.
In this case, a desired molded article can be obtained by a combination of the injection molding related technique and the so-called foam molding technique or expansion molding technique.
In addition, as required, various molding methods such as hollow molding, extrusion molding, compression (press) molding, foaming (expansion) molding, sheet molding, calendar molding, film molding, thermoforming, stamping molding, powder molding, Each molded body can also be obtained.

  Applications of the propylene resin composition of the present invention include various molded products in the field of industrial parts such as automobile parts and parts of household electrical appliances such as televisions, and industrial materials such as pallets and containers, preferably automobile parts. For example, an instrument panel, a door trim, a pillar, a bumper, a door protector, a side protector, a side molding, and the like can be given.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In addition, the physical-property measurement, analysis, etc. in the following examples are according to the following methods, and the following materials were used.

1. Physical property measurement method, analysis method, evaluation method (1) Melt flow rate (MFR)
Based on JIS K7210, it was measured by the method described in this specification.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(3) mm fraction It measured by the method as described in the said specification using JEOL Co., Ltd. make, GSX-400, and FT-NMR.
(4) Elongation viscosity It measured by the method as described in this specification using the rheometer.
(5) Composition analysis A calibration curve was prepared by chemical analysis by the JIS method and measured by fluorescent X-ray.
(6) Flexural modulus: Measured in the following manner in accordance with JIS K-7171 (ISO178).
Testing machine: Precision universal testing machine Autograph AG-20KNG (manufactured by Shimadzu Corporation)
Test piece: length 80 mm, thickness 4 mm, width 10 mm (injection molding)
Test temperature: 23 ° C., distance between fulcrums: 32.0 mm, test speed: 1.0 mm / min (7) IZOD impact strength: Measured according to the following procedure according to IS K-7110.
Testing machine: Digital impact testing machine (manufactured by Toyo Seiki)
Test piece: length 80 mm, thickness 10 mm, width 4 mm, notched (notch depth 2.00 mm, tip radius 0.25 mm, angle 45 °), injection molding Test temperature: 23 ° C.

2. 2. Production of raw materials 2-1. Propylene polymer (a)
[Production Example 1]: (A) -1
(1-1) [Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium]:
Synthesis of (1-1-a) dimethylbis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} silane:
Synthesis was performed according to the method described in Example 1 of JP-A-2004-124044.

Synthesis of (1-1-b) rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium:
In a 100 ml glass reaction vessel, 5.3 g (8.8 mmol) of dimethylbis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} silane and 150 ml of diethyl ether are added, and dry ice-methanol is added. Cooled to -70 ° C in bath. To this, 12 ml (18 mmol) of a 1.50 mol / liter n-butyllithium-hexane solution was added dropwise. After dropping, the temperature was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 200 ml of toluene was added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath.
Thereto was added 2.8 g (8.7 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 3 days while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with dichloromethane / hexane, and racemic dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium. 2.9 g (yield 39%) of yellowish orange crystals (purity 99% or more) was obtained.

The resulting proton nuclear magnetic resonance method for racemate identified value according to ^{(1 H-NMR)} are shown below.
_{^{[1 H-NMR (CDCl 3}} ) Identification Results
Racemate: δ 1.12 (s, 6H), δ 2.42 (s, 6H), δ 6.06 (d, 2H), δ 6.24 (d, 2H), δ 6.78 (dd, 2H), δ 6. 97 (d, 2H), δ 6.96 (s, 2H), δ 7.25 to δ 7.64 (m, 12H).

(1-2) Synthesis of rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium was carried out in the same manner as in Example of JP-A-11-240909. 1 was carried out.

(2) [Catalyst synthesis]:
(2-a) Chemical treatment of ion-exchange layered silicate In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL: average particle size 19 μm) as a layered silicate. ) 600 g was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

During (2-b) Catalyst Preparation and Preliminary polymerization 3 neck flask (volume 1L), placed chemically treated smectite 10g obtained in (2-a), the slurry was added heptane (66 mL), tri thereto Isobutylaluminum (24 mmol: 34 mL of a 140 mg / mL heptane solution) was added and stirred for 1 hour, then washed to 1/100 with heptane, and heptane was added to a total volume of 100 mL.
In another flask (volume 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium ( 0.135 mmol) was dissolved in toluene (38 mL) (complex solution 1).
In another flask (volume 200 mL), rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium (0. 015 mmol) was dissolved in toluene (5 mL) (complex solution 2).

To a 1 L flask containing chemically treated smectite, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added, and the complex solution 1 was added, followed by the addition of the complex solution 2. Stir at room temperature for 60 minutes. Thereafter, 356 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, propylene feed was stopped, and residual polymerization was performed at 50 ° C. for 0.5 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 26.1 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.84.

(3) [Polymerization]
First step polymerization:
The 3 L autoclave was thoroughly dried in advance by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and introducing 350 Nml of hydrogen and 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 150 mg of the prepolymerized catalyst prepared as described above in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 30 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 60 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.7 MPa, and then ethylene was added at a partial pressure of 1.3 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to maintain the total pressure at 2.0 MPa and maintained at 60 ° C.
The average gas composition of the polymerization in the second step was C2: 65.0 mol%. After 70 minutes, polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 380 g of a polymer was obtained.

A part of the obtained sample was melt-kneaded under the following conditions using a lab plast mill (model 50C150) manufactured by Toyo Seiki Co., Ltd.
Polymer: 42 g (1.0 parts of IRGASTAB FS210FF, 0.5 parts of hydrotalcite manufactured by Ciba Geigy)
Temperature: 170 ° C
Rotation speed: 70rpm
Time: 3 minutes The elongation viscosity was measured by the measuring method 1 using the obtained sample.

(4) [High temperature fractionation with orthodichlorobenzene]:
Using orthodichlorobenzene as a solvent, according to the above-described method of temperature rising fractionation, it was separated into a component soluble in 5 ° C. or more and less than 60 ° C. (intermediate component) and a component insoluble in 101 ° C. or more (high temperature component).

  The evaluation results of Production Example 1 (in combination with Production Examples 2 to 3) are shown in Table 1.

[Production Example 2]: (A) -2
(1) [Polymerization]:
First step polymerization:
The 3 L autoclave was thoroughly dried in advance by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 330 Nml of hydrogen and 750 g of liquid propylene were introduced, and the temperature was raised to 75 ° C.
Thereafter, 150 mg of the prepolymerized catalyst prepared as described above in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 30 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the nitrogen-substituted autoclave at 60 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.8 MPa, and ethylene was then added at a partial pressure of 1.2 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to maintain the total pressure at 2.0 MPa and maintained at 60 ° C.
The average gas composition of the polymerization in the second step was C2: 60.0 mol%. After 80 minutes, polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 390 g of a polymer was obtained.

[Production Example 3]: (A) -3
(1) [Catalyst synthesis]:
Synthesis of solid catalyst component (Z) A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified n-heptane was introduced. Further, 250 g of MgCl ₂ and 1.8 L of Ti (On-Bu) ₄ were added, and a reaction was performed at 95 ° C. for 2 hours. The reaction product was cooled to 40 ° C. and 500 ml of methyl hydrogen polysiloxane (20 centistokes) was added. After 5 hours of reaction at 40 ° C., the precipitated solid product was thoroughly washed with purified n-heptane.
Subsequently, purified n-heptane was introduced to adjust the concentration of the solid product to 200 g / L. Here, 300 ml of SiCl ₄ was added and a reaction was carried out at 90 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 100 g / L. A liquid prepared by mixing 30 ml of phthalic acid dichloride with 270 ml of purified n-heptane was prepared in advance, and the mixed liquid was added to an autoclave and reacted at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 200 g / L. To this, 1 L of TiCl ₄ was added and a reaction was carried out at 95 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a slurry of the solid component (ZA1). A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (ZA1) was 2.5% by weight.
Next, a 20 L autoclave equipped with a stirring device was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (ZA1) was introduced as a solid component (ZA1). Purified n-heptane was introduced to adjust the liquid level to 4L. Here, components 25ml trimethylvinylsilane as (ZA2), the component (ZA3) as t-Bu (Me) Si ( OMe) 2 to 20 ml, _Et 3 the n- heptane dilution of _Et 3 Al as the component (ZA4) Al As a result, 40 g was added, and the reaction was performed at 40 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane, and a portion of the resulting slurry was sampled and dried. As a result of analysis, the solid component contained 1.8 wt% Ti and 4.5 wt% t-Bu (Me) Si (OMe) ₂ .
Prepolymerization was performed by the following procedure using the solid component obtained above. Purified n-heptane was introduced into the slurry, and the solid component concentration was adjusted to 20 g / L. After cooled slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 240 g. After the supply of propylene was completed, the reaction was continued for another 30 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a solid catalyst component (Z). This solid catalyst component (Z) contained 2.1 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component (A) excluding polypropylene contained 1.6% by weight of Ti and 4.3% by weight of t-Bu (Me) Si (OMe) ₂ .

(2) [Polymerization]:
First step polymerization:
[Polypropylene polymerization]
A stainless steel autoclave having an internal volume of 3.0 liters having a stirring and temperature control device was heated and dried under a nitrogen flow, cooled to room temperature and substituted with propylene, and then introduced 400 mg of triethylaluminum and 7000 ml of hydrogen, Next, 750 grams of liquid propylene was introduced and the internal temperature was adjusted to 70 ° C., and then 10 milligrams of the above solid catalyst component was injected to polymerize propylene. After 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
30 g of the polymer after the first step was recovered from a nitrogen-substituted autoclave using a Teflon (registered trademark) tube and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 80 ° C. under atmospheric pressure, 700 Nml of hydrogen was added, and then propylene was added to 1.1 MPa in partial pressure, and ethylene was then added to 0.4 MPa in partial pressure. Polymerization of was started. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced and maintained at a total pressure of 1.5 MPa, and maintained at 80 ° C.
After 15 minutes, unreacted ethylene / propylene mixed gas was purged to terminate the polymerization. As a result, 367 g of a polymer was obtained.

2-2. Inorganic filler (b)
The following were used.
Talc-1; fine powder talc having an average particle size = 5.2 μm and an average aspect ratio = 6

2-3. Thermoplastic elastomer (C)
The following were used.
Elastomer-1; MFR = 6.7 g / 10 min, density = 0.864 g / cm ³ , butene content = 32 wt% ethylene-1 butene rubber-like random copolymer

(Examples 1-4)
The propylene-based polymer (I), the inorganic filler (B), and the thermoplastic elastomer (C) were blended in the proportions shown in Table 2, granulated under the following conditions, and evaluated for performance. The evaluation results are shown in Table 3.

1. Additive formulation (1) Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm, Tris (2,4-di-t- Butylphenyl) phosphite 500ppm
(2) Neutralizing agent: 500 ppm calcium stearate

2. Granulation (1) Extruder: Technobel KZW-15-45MG twin screw extruder (2) Screw: 15 mm bore L / D = 45
(3) Extruder set temperature: (from below the hopper) 40, 80, 160, 200, 200, 200 (die temperature)
(4) Screw rotation speed: 400rpm
(5) Discharge amount: Adjusted to about 1.5 kg / hr with a screw feeder (6) Die: 3 mm diameter Strand die Number of holes 2

3. Molding The obtained raw material pellets were injection molded under the following conditions to obtain flat plate test pieces for physical property evaluation.
(1) Standard number: JIS K-7152 (ISO 294-1)
(2) Molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co., Ltd. (3) Molding machine set temperature: (from below the hopper) 80, 210, 210, 200, 200 ° C.
(4) Mold temperature: 40 ° C
(5) Injection speed: 52 mm / s (screw speed)
(6) Holding pressure: 30 MPa
(7) Holding time: 8 seconds (8) Mold shape: Two flat plates (thickness 4 mm, width 10 mm, length 80 mm)

(Comparative Examples 1-2)
Propylene polymer (I), inorganic filler (B), and thermoplastic elastomer (C) were blended in the proportions shown in Table 2 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

  As shown in Table 2 and Table 3, the propylene-based resin compositions having the compositions shown in Examples 1 to 4 that satisfy the respective requirements in the essential constituent elements of the present invention have good fluidity and high rigidity. It has become clear that it has impact strength and molding processability, and has performance suitable for industrial parts and various molded articles, for example, automotive parts such as instrument panels and side protectors.

On the other hand, the propylene-based resin compositions having the compositions shown in Comparative Examples 1 and 2 have poor performance balance.
For example, in Comparative Example 1, since the λmax of the propylene-based polymer (A) (especially the xylene-soluble component (B)) is small, the effect of improving the balance of physical properties is not manifested. There was a large difference in the balance between modulus and IZOD impact strength.
In Comparative Example 2, since the λmax of the propylene-based polymer (A) (especially the xylene-soluble component (B)) is small, the effect of improving the physical property balance is not manifested. There was a large difference in the balance between modulus and IZOD impact strength.

  The propylene-based resin composition of the present invention is excellent in mechanical property balance, has improved melt fluidity, and is excellent in molding processability and molding appearance. It has a performance suitable for being widely used for containers and the like, for example, automobile parts such as instrument panels and side protectors. Therefore, the industrial applicability is very large.

It is a figure of explanation of the base line and section of a chromatogram in GPC It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer.

Claims (6)

It is composed of the following component (A) that is insoluble in p-xylene at 25 ° C. and component (B) that is soluble in p-xylene at 25 ° C., and (i) the weight average molecular weight (Mw) measured by GPC is (Ii) 60 to 98% by weight of a propylene-based polymer (i) having a strain hardening degree (λmax) of 1.1 or more in the measurement of elongational viscosity, and inorganic fillers (b) 1 to 39 A propylene-based resin composition comprising: wt% and thermoplastic elastomer (c) 1 to 39 wt%.
Component (A): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (A1) to (A5).
(A1) 20% by weight to less than 95% by weight with respect to the total amount of the polymer,
(A2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(A3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 93% or more.
(A4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(A5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (B): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (B1) to (B4).
(B1) 5% by weight to less than 80% by weight based on the total amount of the polymer,
(B2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(B3) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(B4) Contains propylene units, ethylene units and / or α-olefin units.   The propylene-based polymer (a) has a branched structure having a crystalline propylene polymer segment in a side chain and an amorphous propylene copolymer segment in a main chain. -Based resin composition.   The propylene system according to claim 1 or 2, wherein the component (A) has a branched structure having a crystalline propylene polymer segment in a side chain and an amorphous propylene copolymer segment in a main chain. Resin composition.   The said component (A) contains an ethylene unit, Comprising: The ethylene content is 0.1 to 10 weight%, The propylene-type resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. object.   The said component (B) contains an ethylene unit, Comprising: Ethylene content is 10 to less than 40 weight%, The propylene-type resin as described in any one of Claims 1-4 characterized by the above-mentioned. Composition.   The propylene-based resin composition according to any one of claims 1 to 5, wherein the thermoplastic elastomer (c) is at least one selected from ethylene-based elastomers.

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