JP4990219B2 - Propylene resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a propylene-based resin composition and a molded article thereof, and more specifically, propylene having good melt processing such as rigidity, impact resistance, and drawdown resistance, improved thermal stability, and excellent recyclability. The present invention relates to a resin composition and a molded body thereof.

  It is important that resins used for hollow molding and extrusion molding have a high melt tension. In general, polypropylene resin is excellent in surface quality such as heat resistance, smoothness, and gloss, but has low melt tension and insufficient draw-down resistance during hollow molding. In particular, when it is used as a hollow molding material of a long molded product with a dimension of 1.3 m or more, such as a large automobile part such as a bumper, a spoiler, and a roof, the thickness becomes non-uniform due to drawdown. The problem becomes obvious.

As a method for improving the melt tension of polypropylene resin, a method of adding a high molecular weight high-density polyethylene having a high melt tension (Patent Document 1), a method of adding a high-density polyethylene having a high melt tension produced by a chromium-based catalyst (Patent Document 2), a method of adding a styrene / conjugated diene block copolymer (Patent Document 3), and the like have been proposed.
However, in the method of adding high density polyethylene, the smoothness of the surface of the molded article is impaired, and it is difficult to say that the properties of the polypropylene resin are sufficiently maintained. In addition, in the method of adding a styrene / conjugated diene block copolymer, there are problems such as parison breakage and uneven thickness of the molded product when it is molded into a product having a complicated shape having a deep drawing part.

Recently, attempts have been made to improve the melt tension by modifying the molecular structure of the polypropylene resin itself. A method of irradiating the polypropylene resin with an electron beam (Patent Document 4), and converting the polypropylene resin into a peroxide. Obtained by prepolymerizing a high-molecular-weight olefin polymer in the presence of an olefin polymerization catalyst, a method of treating with a crosslinking aid (Patent Document 5), a method of copolymerizing propylene and polyene (Patent Document 6). A method of polymerizing propylene in the presence of a prepolymerization catalyst (Patent Document 7) has been proposed.
However, in the method of irradiating the polypropylene resin with an electron beam or the method of treating the polypropylene resin with a peroxide or a crosslinking aid, it is difficult to control the side reaction of higher order crosslinking, and the appearance of the gel is caused Defects and smoothness will be adversely affected. Moreover, in the method of copolymerizing propylene and polyene, the effect of improving the melt tension is not always sufficient, and there is a concern about the generation of gel. Further, in any method of polypropylene resin, there is a problem that the melt tension changes due to the thermal history.

That is, in the molding process, particularly hollow molding, recycling is usually performed by collecting burrs from the viewpoint of environmental problems and economy. However, the burrs that have been subjected to a thermal history once have a melt tension. Therefore, even if the recycling rate is small, it has a non-negligible effect on the melt processing characteristics. Thus, there was a problem in recyclability.
Under such circumstances, the propylene-based resin composition that solves the problems in the prior art, has good melt processing such as rigidity, impact resistance, and drawdown resistance, has improved thermal stability, and is excellent in recyclability. There is a need for early development.

Japanese Patent Laid-Open No. 3-197542 JP-A-8-92438 Japanese Patent Laid-Open No. 7-316361 JP-A-2-298536 WO99 / 27007 International Publication Pamphlet JP-A-5-194778 JP-A-10-231394

  In view of the above-mentioned problems of the prior art, the object of the present invention is a propylene-based resin composition that has excellent melt processing such as rigidity, impact resistance, and drawdown resistance, improved thermal stability, and excellent recyclability. And providing a molded body thereof.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, improved long-term branching having a high degree of strain hardening (λmax) and isotactic triad fraction (mm), which promotes improvement in the balance of physical properties. Type propylene-based polymer and specific resin components blended in a specific ratio, the resulting propylene-based resin composition has good melt processing such as rigidity, impact resistance, and drawdown resistance As a result, it was found that the thermal stability was improved and the recyclability was excellent, and the present invention was completed.

That is, according to 1st invention of this invention, melt flow rate [230 degreeC, 21.18N load] is 0.05-2 g / 10min of crystalline polypropylene (A) 0-79 weight%, From component (α) insoluble in p-xylene at 25 ° C. that satisfies requirements (α1) to (α5) and component (β) that is soluble in p-xylene at 25 ° C. that satisfies the following requirements (β1) to (β3) 20% to 99% by weight of a propylene polymer (B) that is configured and satisfies the following requirements (i) to (iv), a hydrogenated product (c1) of a styrene / conjugated diene block copolymer, Mooney viscosity [ ML1 + 4 (121 ° C.)] 5 or more ethylene / α-olefin copolymer rubber (c2), melt flow rate [230 ° C., 21.18 N load] is 0.3-2 g / 10 min, density is 0 .920g / cm ² or more Propylene resin composition characterized by comprising at least one thermoplastic resin (C) 1 to 50 wt% selected from styrene polymer resin (c3) is provided.
(Α1) 20 to 95% by weight relative to the total amount of propylene polymer (B) (α2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Α3) Isotactic triad fraction (mm) measured by 13C-NMR is 93% or more,
(Α4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(Α5) Contains a propylene unit and an ethylene unit or an α-olefin unit.
(Β1) 5 to 80% by weight based on the total amount of the propylene-based polymer (B),
(Β2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Β3) Contains a propylene unit, an ethylene unit and / or an α-olefin unit.
(I) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Ii) The component insoluble in hot p-xylene is 0.3% by weight or less,
(Iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more.
(Iv) Melt flow rate [230 degreeC, 21.18N load] is 0.05-20 g / 10min.

  According to the second invention of the present invention, in the first invention, the component (β) further has (β4) a strain hardening degree (λmax) of 2.0 or more in the measurement of elongational viscosity. A propylene-based resin composition is provided.

  According to the third invention of the present invention, in the first or second invention, the propylene polymer component (B) has a crystalline propylene polymer segment in the side chain, and an amorphous propylene copolymer segment. A propylene-based resin composition characterized by having a branched structure having a main chain in the chain is provided.

  According to a fourth invention of the present invention, in any one of the first to third inventions, the component (α) has a crystalline propylene polymer segment in a side chain, and an amorphous propylene copolymer segment. A propylene-based resin composition characterized by having a branched structure having a main chain in the chain is provided.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the component (α) contains an ethylene unit, and the ethylene content is 0.1 to 10% by weight. A propylene-based resin composition is provided.

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, the component (β) contains an ethylene unit and has an ethylene content of 10 to 60% by weight. A propylene-based resin composition is provided.

  Moreover, according to 7th invention of this invention, the blow molding body which consists of a propylene-type resin composition of the invention in any one of 1st-6th is provided.

  The propylene-based resin composition of the present invention is remarkably improved in draw-down resistance, physical property balance, surface smoothness and thermal stability (return property) of the molded product during hollow molding. Therefore, when extrusion molding or blow molding is used with this, a hollow molded body having a large and complicated shape becomes possible, which is suitable for automobile exterior parts such as bumpers.

  As described above, the propylene-based resin composition of the present invention has a predetermined melt flow rate (hereinafter referred to as MFR) of 0 to 79% by weight of crystalline polypropylene (A), the following components (α) and components (β And satisfying the requirements (i) to (iv) described above, that is, the weight average molecular weight (Mw), the amount of thermal p-xylene insoluble component, the strain hardening degree (λmax) and MFR in the measurement of elongational viscosity are 20 to 99% by weight of the propylene-based polymer (B), a hydrogenated product of styrene / conjugated diene block copolymer (c1), an ethylene / α-olefin copolymer rubber having a predetermined Mooney viscosity ( c2), or at least one thermoplastic resin (C) selected from an ethylene polymer resin (c3) having a predetermined MFR and density.

Component (α): A component (CXIS) that satisfies the following requirements (α1) to (α5) and is insoluble in p-xylene at 25 ° C.
(Α1) 20 to 95% by weight relative to the total amount of propylene polymer (B) (α2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Α3) Isotactic triad fraction (mm) measured by 13C-NMR is 93% or more,
(Α4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(Α5) Contains a propylene unit and an ethylene unit or an α-olefin unit.
Component (β): Component (CXS) that satisfies the following requirements (β1) to (β3) and is soluble in p-xylene at 25 ° C.
(Β1) 5 to 80% by weight based on the total amount of the propylene-based polymer (B),
(Β2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Β3) Contains a propylene unit, an ethylene unit and / or an α-olefin unit.
Hereafter, each component of the propylene-type resin composition of this invention, manufacture of the resin composition, a molded object, etc. are demonstrated in detail.

[I] Components of propylene-based resin composition Component (A): Crystalline polypropylene Examples of the crystalline polypropylene used in the present invention include a propylene homopolymer, a random copolymer or a block copolymer of propylene and another α-olefin such as ethylene and butene-1. These can be used, and these can be used in combination.
The crystalline polypropylene used in the present invention has an MFR (measured at JIS K7210, 230 ° C., 21.18 N load) of 0.05 to 2 g / 10 minutes, preferably 0.1 to 1.5 g / 10 minutes, more preferably. Is 0.2 to 1.2 g / 10 min. If it is less than the lower limit, the melt ductility is lowered, and if it exceeds the upper limit, the drawdown resistance is lowered.

In the present invention, crystallinity means having an endothermic peak based on crystal melting in DSC measurement, and preferably means an endothermic amount of 30 J / g or more. Here, the peak value of the melting temperature means the peak of the endothermic curve obtained by a differential scanning calorimeter (DSC). For example, a DSC7 model manufactured by PerkinElmer is used as a measurement method, and a sample of about 10 mm is heated from 0 ° C. to 230 ° C. at a temperature increase rate of 20 ° C./minute, held for 3 minutes, and then 5 ° C./minute. The temperature is lowered to 0 ° C. at a temperature lowering rate, held for 5 minutes, and then the peak temperature of the endothermic curve obtained when the temperature is raised to 230 ° C. at a temperature rising rate of 20 ° C./min is obtained.
The crystalline polypropylene (A) used in the present invention preferably has an endothermic curve peak temperature of 145 to 170 ° C.

  The crystalline polypropylene resin (A) used in the present invention has a strain hardening degree (λmax) in the measurement of elongational viscosity of preferably less than 2.0, more preferably less than 1.5. By doing so, the appearance of the molded product is excellent and the economy is improved. The details of the method for measuring the strain hardening degree (λmax) in the measurement of the extensional viscosity will be described later.

2. Component (B): Propylene Polymer (2-1) Characteristics of Component (B) Component (B) used in the present invention is composed of component (α) that is insoluble in p-xylene at 25 ° C. and p at 25 ° C. A component composed of a component (β) that is soluble in xylene, and (i) a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000, and (ii) a component that is insoluble in hot p-xylene Is 0.3% by weight or less, (iii) the strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more, and (iv) the melt flow rate [230 ° C., 21.18 N load] is 0.1. It is a propylene-type polymer characterized by being 05-20 g / 10min.

  The component (B) includes a crystalline propylene polymer component and a propylene-ethylene random copolymer including a copolymer in which a part of the crystalline propylene polymer segment and the amorphous propylene copolymer segment are chemically bonded. A propylene-ethylene copolymer obtained by sequentially producing the coalescence component by multistage polymerization is preferred.

The multistage polymerization is preferably a two-stage polymerization in which the crystalline propylene polymer component is polymerized in the first stage and the propylene-ethylene random copolymer component is polymerized in the second stage.
The presence of a part of the crystalline propylene polymer produced in the first step that stops the reaction in the state of the terminal vinyl group allows the crystallinity of the terminal vinyl when the second-stage polymerization is carried out as it is. A branched structure in which the propylene polymer is a macromonomer, involved in the second stage polymerization, the amorphous propylene copolymer segment (propylene-ethylene random copolymer segment) is the main chain, and the crystalline propylene polymer segment is the side chain A copolymer having

  The present inventors consider that the factor that the addition of the component (B) exhibits a good melt tension can be attributed to the presence of this branched structure. In general, a polymer having a part composed of a chain of different monomers in one molecule, such as a real block copolymer or a graft copolymer, is a molecule that is considerably smaller than an ordinary phase separation structure, called a microphase separation structure. It is known to have a phase separation structure on the order of level, and such a fine phase separation structure is considered to significantly improve the melt tension. Actually, in the electron micrographs (FIGS. 1 and 2) of the component (B) (copolymer having a branched structure) according to the present invention, compared with a normal resin (one having no branched structure (FIG. 3)). A very fine dispersion structure of rubber domains is observed, which supports the above inference.

  The component (B) includes a copolymer having a branched structure in which an amorphous propylene copolymer segment (propylene-ethylene random copolymer segment) is a main chain and a crystalline propylene polymer segment is a side chain. Yes. As a component constituting the main chain, in addition to propylene and ethylene, other unsaturated compounds, for example, α-olefins such as 1-butene may be included within a range not impairing the effects of the present invention. The component constituting the side chain is mainly propylene, and may contain a small amount of other unsaturated compounds, for example, α-olefins such as ethylene and 1-butene, as long as the essence of the present invention is not significantly impaired. .

One of the methods for determining whether or not a graft copolymer in which the propylene-ethylene random copolymer component is a main chain and the crystalline propylene polymer component is a side chain is as follows: It is effective to use the strain hardening degree (λmax) obtained from the measurement of the viscosity.
The strain hardening degree (λmax) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension.
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.
In component (B), a propylene polymer having a terminal vinyl group is involved in the polymerization as a macromonomer during the production of the first-stage crystalline propylene polymer, and a branched propylene polymer is produced. Therefore, this degree of strain hardening is an index of the amount of terminal vinyl propylene polymer produced, and is preferably 1.1 or more.
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 elongational viscosity ηE (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain becomes 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity.
FIG. 4 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 (Me) of 7000 or more of polypropylene is preferred as the branch length, and that the degree of strain hardening increases as the branch length increases.

Component (B) is separated into a crystalline component and an amorphous component, and the amount of component (β) dissolved in paraxylene at 25 ° C. is 5 to 80% by weight based on the total amount of component (B), The amount of the component (α) insoluble in xylene is 20 to 95% by weight.
Here, a specific method for separating the crystalline component and the amorphous component is as follows.

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.

  As described above, the component (B) is composed of a crystalline component (α) and an amorphous component (β), and a part of each component is composed of a propylene-ethylene random copolymer segment as a main chain. And the following characteristics (i) to (iv), (α1) to (α5), (analytical) include a copolymer having a branched structure in which the crystalline propylene polymer segment is a side chain. Characterized as having [beta] 1) to ([beta] 3).

(I): The weight average molecular weight (Mw) measured by GPC of a component (B) is 100,000-1 million.
(Ii): The amount of the component (B) insoluble in hot paraxylene is 0.3% by weight or less based on the total amount of the component (M).
(Iii): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (B) is 1.1 or more.
(Iv) Melt flow rate [230 degreeC, 21.18N load] is 0.05-20 g / 10min.

(Α1): The amount of component (α) is 20 to 95% by weight based on the total amount of component (B).
(Α2): The weight average molecular weight (Mw) measured by GPC of the component (α) is 100,000 to 1,000,000.
(Α3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (α) is 93% or more.
(Α4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (α) is 2.0 or more.
(Α5): Contains a propylene unit and an ethylene unit or an α-olefin unit.

(Β1): The amount of component (β) is 5 to 80% by weight based on the total amount of component (B).
(Β2): The weight average molecular weight (Mw) measured by GPC of the component (β) is 100,000 to 1,000,000.
(Β3): Contains propylene units, ethylene units and / or α-olefin units.

Hereinafter, each of the above characteristics will be sequentially described.
(I): The weight average molecular weight (Mw) measured by GPC of a component (B) is 100,000-1 million.
As the component (B), those having a weight average molecular weight in the range of 100,000 to 1,000,000 are used.
The weight average molecular weight (Mw) is measured by a GPC measuring apparatus and conditions described later, and it is necessary that the Mw of the component (B) is in the range of 100,000 to 1,000,000. If this Mw is smaller than 100,000, the moldability is inferior and the mechanical strength is insufficient. On the other hand, if Mw exceeds 1,000,000, the melt viscosity is high and the moldability is lowered. From the balance of moldability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 180,000 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

(Ii): The component (B) insoluble in hot p-xylene is 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. If the component insoluble in hot p-xylene exceeds 0.3% by weight, the appearance of the molded product is inferior and the thermal stability (returnability) is lowered.
In the present invention, the component insoluble in hot p-xylene needs to be 0.3% by weight or less. A method for measuring a component insoluble in hot p-xylene is as follows.
A glass separable flask equipped with a stirrer is charged with 500 mg of a polymer in a bowl made of stainless steel 400 mesh (wire diameter 0.03 μm, aperture 0.034 mm, space ratio 27.8%). Fixed to. 700 ml of p-xylene containing 1 g of an antioxidant (BHT: 2,6-di-t-butyl-4-methylphenol) was added, and the polymer was dissolved while stirring at a temperature of 140 ° C. for 2 hours.
The soot containing the p-xylene insoluble part was collected, sufficiently dried and weighed to obtain the paraxylene insoluble part. The gel fraction (wt%) defined as the hot p-xylene insoluble part was calculated by the following formula.
Gel fraction = [(residual amount in mesh g) / (prepared sample amount g)] × 100

Further, in order to have a small amount of gel or no gel as described above, it is important that there are no components having a very high molecular weight. 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.
Therefore, the Q value (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) measured by GPC is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.
Moreover, in order not to extend extremely to the high molecular weight side, it is necessary that the molecular weight M (90) at which the integrated 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 this M (90) exceeds 2,000,000, the high molecular weight component is excessively increased, gel is generated, and the appearance of the molded product is impaired, or the molding processability is lowered. Therefore, M (90) is 2,000,000 or less, preferably 1,500,000 or less, and more preferably 1,000,000.

(Iii): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (B) is 1.1 or more.
The physical significance of the strain hardening degree is as described above. If this value is large, uneven thickness is unlikely to occur during molding. Therefore, the strain hardening degree needs to be 1.1 or more, preferably 1.5 or more, more preferably 2.0 or more, and further preferably 4.0 or more.
The length of branching is preferably an entanglement molecular weight of 7000 or more of polypropylene. Strictly speaking, this molecular weight is different from the weight average (Mw) measured by GPC. Therefore, the weight average molecular weight (Mw) value measured by GPC is preferably 15000 or more, and more preferably 30000 or more.

(Iv) Melt flow rate [JIS K7210, 230 ° C., 21.18 N load] is 0.05 to 20 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes, more preferably 0.1 to 5 g / 10. Minutes. When this MFR is smaller than 0.05 g / 10 min, the melt ductility is lowered, and when it exceeds the upper limit, the drawdown resistance is lowered.

(Α1): The amount of component (α) is 20 to 95% by weight, preferably 30 to 94% by weight, more preferably 40 to 93% by weight, based on the total amount of component (B).
This regulation is a range of the component (α) with respect to the total amount of the component (B), and a component in this range is used from the balance of rigidity and impact resistance.

(Α2): The weight average molecular weight (Mw) measured by GPC of the component (α) 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 the crystalline component (α) in the component (B) has a weight average molecular weight of 100,000 to 1,000,000. Ranges are used.
If this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, if Mw exceeds 1,000,000, the melt viscosity is high and the melt ductility is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is in the range of 200,000 to 900,000, more preferably in the range of 210,000 to 800,000.

(Α3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (α) is 93% or more.
The crystalline component (α) of the component (B) according to the present invention has a stereoregularity in which the mm fraction of propylene unit 3 chain 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 steric 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 (α) 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 assignment is performed according to the method described in detail in Japanese Patent Application No. 2006-311249, with reference to Macromolecules, (1975) 8 pp. 687, and Polymer, Vol. 30, p. 1350 (1989). .

(Α4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (α) is 2.0 or more.
The strain hardening degree (λmax) of the component (α) is 2.0 or more, preferably 3.0 or more, more preferably 4.0 or more.
The length of branching is preferably an entanglement molecular weight of 7000 or more of polypropylene. Moreover, as a weight average (Mw), it is 15000 or more, More preferably, it is 30000 or more.

(Α5): Contains a propylene unit and an ethylene unit or an α-olefin unit.
As a unit constituting the crystalline component (α), 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 less than 120 ° C., the rigidity is inferior, so that it is unsuitable for industrial members. The ethylene content of the component (α) is preferably 0.1 to 10% by weight, more preferably 0.2%. -7% by weight, more preferably 0.3-5% by weight.
The ethylene unit is measured according to the method described in Macromolecules 1982 1150 using ¹³ C-NMR.

(Β1): The amount of component (β) is 5 to 80% by weight, preferably 6 to 70% by weight, more preferably 7 to 60% by weight based on the total amount of component (B).
This regulation is a range of the component (β) with respect to the total amount of the component (B), and a component in this range is used from the balance of rigidity and impact resistance.

(Β2): The weight average molecular weight (Mw) measured by GPC of the component (β) 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 the amorphous component (β) in the component (B) has a weight average molecular weight of 100,000 to 100. Thousands of things are used.
If this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, if Mw exceeds 1,000,000, the melt viscosity is high and the melt ductility is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.

(Β3): Contains propylene units, ethylene units and / or α-olefin units.
As a unit constituting the amorphous component (β), 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 preferable not to contain an (alpha), (omega) -diene unit.
The kind of comonomer is preferably ethylene or a linear α-olefin, more preferably ethylene, and the ethylene content is usually 10% by weight or more and 60% by weight or less. From the viewpoint of improving impact resistance at low temperatures, those having a weight of 40 wt% or more and 60 wt% or less are preferred.
The component (β) preferably satisfies the following (β4) in addition to the above (β1) to (β3).

(Β4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (β) is 2.0 or more. As described above, when the value of the strain hardening degree (λmax) is large, uneven thickness is formed during molding. It is hard to occur. Therefore, the strain hardening degree (λmax) is preferably 2.0 or more, more preferably 2.5 or more and 20 or less.

(2-2) Production method of component (B) The component (B) according to the present invention is capable of producing a macromer having a vinyl terminal, and further comprising a catalyst system capable of copolymerizing the macromer with propylene and ethylene. It can be manufactured by using.
Among them, using a polymerization catalyst obtained by contacting the catalyst components (a), (b) and (c) described below,
(I) first step of polymerizing propylene alone, or propylene and ethylene or α-olefin, and polymerizing ethylene or α-olefin with respect to all monomer components in an amount of 0 to 10% by weight; and (ii) propylene and ethylene Or a second step in which α-olefin is polymerized and ethylene is polymerized in an amount of 10 to 70% by weight based on the total monomer components;
By the process which has, it can manufacture with sufficient 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 R ₁ is independently hydrogen, 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 carbon. 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 two R ₁ is carbon A heterocyclic group containing nitrogen, oxygen, or sulfur of several 4 to 16 is shown. Two R _{1 s} may be the same or different from each other. Each R ₂ 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 an aryl group having 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. Two R ₂ may be the same as or different from each other.
X and Y 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 hydrocarbon having 1 to 20 carbon atoms. Represents a 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 is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom Represents a silylene group, an oligosilylene group, or a germylene group which may have ˜20 hydrocarbon groups.

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ₁ is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted 2 group. -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.
R ₁ is particularly preferably a 2- (5-methyl) -furyl group. Moreover, it is preferable that two R ₁ are mutually the same.

R ₂ is 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. Such an aryl group has 6 to 16 carbon atoms. 1 or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogen-containing hydrocarbon groups having 1 to 6 carbon atoms on the aryl cyclic skeleton. You may have as a substituent.
R ₂ is preferably at least one of phenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-dit-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group. , A naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-t-butylphenyl group, or a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In general formula (1), X and Y each independently represent 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 a carbon number of 1 to 20 A silicon-containing 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. 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 general formula (1), Q is a divalent hydrocarbon group having 1 to 20 carbon atoms and a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, which binds two five-membered rings. , Either 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 include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di ( n-propyl) silylene, di (i-propyl) silylene, alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group It can be mentioned. 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.
Dimethylsilylenebis (2- (2-furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-thienyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, diphenylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylenebis (2- (2- (5-Methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylenebis (2- (2- (5-methyl) -thienyl) -4-phenyl-indenyl) hafnium Dichloride, dimethylsilylenebis (2- (2- (5-t Butyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-phenyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (4,5-dimethyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene Bis (2- (2-benzofuryl) -4-phenyl-indenyl) hafnium dichloride, diphenylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis ( 2- (2- (5-Methyl -Furyl) -4-methyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-isopropyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furfuryl) ) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-chlorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-Methyl) -furyl) -4- (4-fluorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-trifluoromethyl) Phenyl) -indenyl) hafnium dichloride, dimethylsilylenebi (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (1-naphthyl) ) -Indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (2-phenanthryl) ) -Indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl)- 4- (1-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 (5-Methyl) -furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (2-phenanthryl) -indenyl) Hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -Furyl) -4- (1-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, Dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4- (2-phenanthryl) -indene ) Hafnium dichloride, dimethylsilylene bis (2- (2- (5-t-butyl) -furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) ) (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) (2- (2- (5-methyl)- And thienyl) -4-phenyl-indenyl) hafnium dichloride.

Of these, more preferred are dimethylsilylene bis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylene bis (2- (2- (5-methyl). ) -Thienyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-chlorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2 -(2- (5-methyl) -furyl) -4-naphthyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -Indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) ( - (2- (5-methyl) - furyl) -4-phenyl - indenyl) hafnium dichloride.
Also particularly preferred are dimethylsilylene bis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene bis (2- (2- (5-methyl) -furyl). ) -4-naphthyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -indenyl) hafnium dichloride.

(2) Catalyst component (b):
Next, the catalyst component (b) is an ion-exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces in which ionic bonds and the like are stacked in parallel with each other by a binding force. A silicate compound having a crystal structure and containing exchangeable ions. 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, a raw material refers to the silicate of the previous stage which performs the chemical process mentioned later. The silicate is not limited to a natural product, and may be an artificial synthetic product.
In addition, if it has ion exchange properties before chemical treatment, silicates whose physical and chemical properties have been changed by the treatment and the ion exchange properties and layer structure have been lost are also ion exchange layered. Treat as 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 component (b) in the raw slurry liquid 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. . 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 the 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 quoted. 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 includes the catalyst component (a), the catalyst component (b), and the catalyst component (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 catalyst component (a), catalyst component (b) and catalyst component (c) used is arbitrary, but the ratio of the transition metal in catalyst component (b) to aluminum in catalyst component (c) is The catalyst component (a) is preferably brought into contact so as to be 0.1 to 1000 (μmol): 0 to 100,000 (μmol) per 1 g. In addition to the catalyst component (a), other types of complexes can be used for the purpose of more efficiently producing a propylene-based copolymer.
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 polymer having a higher molecular weight than the catalyst component (a).
As a particularly preferred metallocene compound, a catalyst component (a-2) represented by the following general formula (2) can be mentioned.

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 co-catalyst of the catalyst component [b] to generate 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.

  In addition to the catalyst component (a), when using another type of catalyst component (a-2) represented by the above formula (2), the total of the catalyst component (a) and the catalyst component (a-2) The ratio of the amount of the catalyst component (a-2) to the amount is arbitrary as long as it satisfies the characteristics of the propylene polymer, but is preferably 0.01 to 0.7. 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, The range is from 0.10 to 0.60, and more preferably from 0.2 to 0.5.

  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.

(5) 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 speed or in a constant pressure state, 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 or a solid of an inorganic oxide such as silica or titania at the time of contacting or after contacting each of the above catalyst 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.

(6) 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, in order to obtain the compound having the molecular weight and molecular weight distribution disclosed in the present invention, the first step is carried out by bulk polymerization and the second step is carried out by gas phase polymerization, or both the first step and the second step are carried out. It is preferable to carry out by phase polymerization.

[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 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.

[Second step]:
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C. In addition, hydrogen can be used as a molecular weight regulator. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Here, the produced propylene-ethylene (or α-olefin) copolymer 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 considered that a polymer having a branched structure having a polymer 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 of the present invention.
Therefore, in order to control the λmax of the CXS component to 2 or more, it is preferable that the ethylene content is 10 wt% to less than 40 wt%, in order to produce a polymer having a desired composition using ethylene as a comonomer. Therefore, it is necessary to control the ethylene gas composition in the gas phase to 10 mol% or more, preferably 15 mol% or more, and 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.
Conversely, when the ethylene content is 40 wt% to 60 wt%, the λmax of the CXS component becomes less than 2, and when ethylene is used as a comonomer, it is necessary to control the ethylene gas composition in the gas phase to 50 mol% or more. Yes, preferably 60 mol% or more, more preferably 65 mol% or more. Moreover, regarding an upper limit, it is 90 mol% or less, Preferably it is 87 mol% or less, More preferably, it is 85 mol% or less.
The propylene polymer (X) according to 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) a component insoluble in hot p-xylene. (Iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more, and the crystalline segment is grafted as a side chain to the amorphous segment. Including polymers. In particular, such graft copolymers are present in the CXIS component (A). Polymerization mechanism in which the crystalline segment becomes a side chain and the non-crystalline segment becomes the main chain, in which the macromer of the crystalline component is produced in the first stage and copolymerized with the amorphous component in the second stage. From the point of view, it is natural.

3. Ingredient (C)
In the propylene-based resin composition of the present invention, in addition to the components (A) and (B), a hydrogenated product (c1) of a specific styrene / conjugated diene block copolymer described below (hereinafter simply referred to as “component (A)”). (Sometimes abbreviated as “component (c1)”), ethylene / α-olefin copolymer rubber (c2) (hereinafter, sometimes simply abbreviated as “component (c2)”), or ethylene polymer resin (C3) (hereinafter sometimes simply referred to as “component (c3)”) at least one thermoplastic resin (C) (hereinafter also simply referred to as “component (C)”). Used as an essential component. At least one component (C) is appropriately added depending on the use. By adding the component (c1), low temperature impact properties and melt tension can be improved. Addition of “component (c2)” can improve low-temperature impact properties. By adding “component (c3)”, the melt tension can be improved.

(1) Component (c1): Hydrogenated product of styrene / conjugated diene block copolymer The hydrogenated product of styrene / conjugated diene block copolymer used in the present invention is a block using butadiene, isoprene or the like as the conjugated diene. This is a hydrogenated copolymer, such as styrene / ethylene / butylene / styrene (SEBS) or styrene / ethylene / propylene / styrene (SEPS), as well as hydrogenated block copolymer of styrene, butadiene and isoprene. There are things. Here, styrene derivatives such as α-methylstyrene and p-methylstyrene can also be used as styrene.
By blending a hydrogenated product of these styrene / conjugated diene block copolymers, the melt tension is improved and the drawdown resistance in hollow molding is improved, which is very effective for large-scale hollow molding. However, this blending reduces the melt fracture rate and makes it difficult to stretch, so in the case of hollow molding with a large blow ratio such as a deep-drawn shape or a complicated shape mold, the spreadability such as parison tearing or uneven thickness of the molded product is reduced. In addition to problems, it is not preferable to add a large amount because the economical efficiency of the composition is impaired.
The hydrogenated styrene / conjugated diene block copolymer used here is not particularly limited as long as a hollow molded body satisfying the above-mentioned requirements can be obtained, but the density in ISO 2781 is 0.90 to 0.90. It is preferably 0.92 g / cm ³ , a styrene content of 31 to 35% by weight, and a viscosity (1 to 2 Pa · s) according to the BMS0380 method.

(2) Component (c2): Ethylene / α-olefin copolymer rubber In the present invention, ethylene / α-olefin copolymer rubber can be added for improving paintability and the like.
The ethylene / α-olefin copolymer rubber used in the present invention is a copolymer rubber using propylene, butene-1, hexene-1, octene-1, etc. as an α-olefin, and as a third component. It may be a terpolymer rubber (so-called EPDM) containing a non-conjugated diene such as ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene and the like. The Mooney viscosity [ML1 + 4 (121 ° C.)] (based on ASTM D1646) of these ethylene / α-olefin copolymer rubbers is 5 or more, preferably 10 or more, more preferably 20 to 40. If the Mooney viscosity is in the above range, it is preferable that the drawdown resistance of the composition is deteriorated and the shapeability at the time of molding is suppressed.
The density of the ethylene · alpha-olefin copolymer rubber used in the present invention is preferably 0.890 g / cm ³ or less, more preferably 0.885 g / cm ³ or less.

(3) Component (c3): Ethylene polymer resin As the ethylene polymer resin used in the present invention, in addition to the ethylene homopolymer, other main components such as ethylene, butene-1, and hexene-1 are used. Examples include copolymers with monomers, and specific examples include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. The ethylene polymer resin is effective in improving the drawdown resistance.
From the viewpoint of the surface quality and paintability of the molded product, an ethylene polymer resin having an MFR (JIS-K6760, 230 ° C., 21.18 N load) of 0.3 to 2 g / 10 min and a density of 0.920 g / cm ³ or more is used. preferable. In particular, a high density polyethylene having an MFR (JIS-K6760, 230 ° C., 21.18 N load) of 0.3 to 2 g / 10 minutes and a density of 0.940 g / cm ³ or more is preferable.

4). Compounding amount of component The compounding amount of the component (A), (B), (C) is 0 to 79% by weight of the crystalline polypropylene of component (A), and the propylene polymer of component (B). Is 20 to 99% by weight and component (C) is 1 to 50% by weight (the total amount of component (A), component (B) and component (C) is 100% by weight), preferably component (A) Is 0 to 70 wt%, component (B) is 20 to 95 wt%, component (C) is 2 to 40 wt%, more preferably component (A) is 0 to 65 wt%, and component (B) is It is 25 to 95% by weight, and the component (C) is 3 to 35% by weight.
Here, when there is too much compounding quantity of a component (A), melt tension will fall and it cannot shape | mold. When there are too few compounding quantities of a component (B), drawdown resistance and spreadability will fall. When there are too few compounding quantities of a component (C), drawdown resistance and low temperature impact property will fall. If the amount of component (C) is too large, the melt ductility deteriorates, the flexural modulus may decrease, and the appearance may be poor.

5. Other Components In the present invention, an inorganic filler (D) (hereinafter sometimes simply referred to as “component (D)”) may be blended as necessary. The addition of the inorganic filler is effective in terms of the heat resistance rigidity of the molded product.
Examples of the inorganic filler include talc, mica, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, molybdenum sulfide, carbon black, glass fiber, carbon fiber, potassium titanate fiber, titanium oxide, clay, and kaolin. Examples thereof include plates such as alumina, silica and hollow glass spheres, needles, granules and fibers. Two or more of these may be used in combination, but talc is particularly preferable. These inorganic fillers can be used after being surface-treated with various organic silanes, titanates and the like in order to improve the affinity with the resin component.

  Furthermore, in the present invention, in addition to the above components (A) to (C), other components can be blended for other purposes within a range not significantly impairing the effects of the present invention. Examples of such other components (arbitrary components) include butene polymer resins, other polyolefins such as 4-methylpentene-1 polymer resins, thermoplastic resins such as polyamide and polyester, and conjugated diene copolymer. Other elastomers such as united rubber and styrene / conjugated diene copolymer rubber, inorganic fillers, antioxidants, UV absorbers, light stabilizers, lubricants, lubricants, plasticizers, thickeners, antistatic agents, difficult Various additives such as a flame retardant, a workability improver, a colorant, a nucleator, a molecular weight modifier, and a paint improver can be exemplified. These components may be added to the composition or may be added to each component.

[II] Production of resin composition for hollow molding The resin composition for hollow molding of the present invention contains the above components (A) to (C), and optionally other components, such as a high-speed mixer, It is generally obtained by heat-melt kneading using a conventional mixing kneader such as a Banbury mixer, continuous kneader, single or twin screw extruder, roll, Brabender plastograph and the like. At this time, a granulation method is usually employed.

[III] Production of Hollow Molded Body The resin composition obtained in this manner is molded into a hollow molded body by an ordinary hollow molding machine. In particular, the effect of the present invention is effectively exhibited when formed into a large hollow molded body having a dimension of 1.3 m or more.
The large hollow molded article is suitably used for parts and products such as automobile bumpers and construction equipment roofs.

  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 a following example follow the following method.

1. Physical property measurement method, analysis method, evaluation method (1) Melt flow rate (MFR)
According to JIS K7210A method and condition M, measurement was performed under the following conditions.
Test temperature: 230 ° C., nominal load: 2.16 kg, die shape: diameter 2.095 mm, length 8.000 mm. The unit is g / 10 minutes.
(2) Weight average molecular weight (Mw)
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. The unit is%.
(4) Elongation viscosity It measured by the method as described in this specification using the rheometer.
(5) Melting temperature (Tm):
Measurements were made using a Seiko DSC.
After taking 5.0 mg of sample and holding it at 200 ° C. for 5 minutes, it is crystallized at a rate of temperature decrease of 10 ° C./min to 40 ° C. to erase its thermal history and further melted at a rate of temperature increase of 10 ° C./min. The peak temperature of the melting curve is taken as the melting point. When a plurality of melting points are observed in the resin, the one observed at the highest temperature is taken as the melting point of the resin.
(6) Quantification of ethylene content The ethylene content is measured by ¹³ C-NMR under the same conditions as in the mm measurement described above. The ethylene content is calculated according to the analysis method described in Macromolecules 1982 1150.
(7) Amount of components insoluble in hot paraxylene Measured by the method described in this specification.

(8) Melt tension (MT) (unit: cN): Using a Capillograph manufactured by Toyo Seiki Co., Ltd., the resin was put into a cylinder with a diameter of 10 mm heated to 230 ° C. and melted at a pushing speed of 10.0 m / min. The resin extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm was taken out at a speed of 4.0 m / min, and the melt tension was measured as an index of resistance to drawdown. In order to form a large blow product, the melt tension is preferably 8 cN or more.
(9) Draw-down resistance: Automotive bumper with a resin temperature of 220 ° C, length of 2.2m, width of 0.4m, and weight of 8kg using Plako DA-100 type large blow molding machine. When the ratio of the upper wall thickness to the lower wall thickness of the molded body was 0.8 to 1.0, the one with less than 0.8, or the molding failure or the molding failure was judged as defective.

(10) Flexural modulus: measured in accordance with JIS K7203 at a bending speed of 2 mm / min at 23 ° C. The product physical property is preferably 1000 MPa or more.
(11) Izod impact strength: Measured with a notch at a temperature of −30 ° C. in accordance with JIS-K7110. The product physical property is preferably 4 kg / cm ² or more. Preferably, it is 5 kg / cm ² or more.
(12) Thermal stability (return property): Using a Plako DA-100 type large blow molding machine, the resin temperature is 220 ° C., the length is 2.2 m, the width is 0.4 m, and the weight is 8 kg. Molded automotive bumper. The bumper was pulverized with a pulverizer and again molded with a large blow molding machine. The product that can be commercialized even if it is repeated 5 times or more is marked as ◎, the product that can be commercialized even if it is repeated 3 times or more and less than 5 times, the product that can be commercialized even if it is repeated 2 or more times but less than 3 times, x Those that could not be made into a product once were designated as xx.

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

Synthesis of (1-b) rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride:
In a 100 ml glass reaction vessel, 5.3 g (8.8 mmol) of dimethylbis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) silane and 150 ml of diethyl ether were added, and dry ice was added. -It cooled to -70 degreeC with the methanol 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 from dichloromethane / hexane, and racemic dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (purity 99% or more). ) Was obtained as yellow-orange crystals (2.9 g, yield 39%).

The resulting proton nuclear magnetic resonance method for racemate identified value according to ^{(1 H-NMR)} are shown below.
^[1 H-NMR (CDCl3) identification result]
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).

(2) [Catalyst synthesis]:
(2-1) Chemical treatment of ion-exchangeable layered silicate 96% sulfuric acid (1044 g) was added to 3456 g of distilled water in a separable flask, 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].

(2-2) Catalyst Preparation and Prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was added, and heptane (114 mL) was added to form a slurry, to which triethylaluminum (50 mmol: 81 mL) of a heptane solution having a concentration of 71 mg / mL was added and stirred for 1 hour, washed with heptane to a residual liquid ratio of 1/100, and heptane was added so that the total volume became 200 mL.
In another flask (volume 200 mL), heptane (85 mL) was added to rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (0.3 mmol). Then, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution with a concentration of 140 mg / mL) was added and stirred for 45 minutes at room temperature to cause a reaction. This solution was added to a 3 L flask containing chemically treated smectite and stirred at room temperature for 45 minutes. Thereafter, 214 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 20 g / hour and prepolymerization was performed while maintaining the temperature at 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, the prepolymerized catalyst was washed by adding decantation again with heptane. Triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the portion remaining after the decantation, and the mixture was stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 47.6 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 1.38.

(1) [Polymerization]:
First step polymerization:
The 3 L autoclave was thoroughly dried beforehand by circulating nitrogen under heating, and then the interior 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 750 g of liquid propylene, the temperature was raised to 70 ° C. Thereafter, 210 mg of the prepolymerized catalyst in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° 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.
12 g of the polymer after the first step was collected from a nitrogen-substituted autoclave using a Teflon (registered trademark) tube and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, the second step polymerization was started by quickly adding 0.5 MPa and then ethylene at a partial pressure of 1.5 MPa. 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 2.0 MPa and maintained at 50 ° C. The average gas composition of the polymerization in the second step was C2: 72.5%. After 2 hours, the unreacted ethylene / propylene mixed gas was purged to stop the polymerization, and 211 g of a polymer (LCB-1) 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.
The value of strain hardening λmax of this sample is 2.5, and it is considered that a graft copolymer is formed.

[Polymerization Example 2]:
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 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 250 mg of the prepolymerized catalyst prepared in Polymerization Example 1 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, 24 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 70 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.5 MPa, and then ethylene was added at a partial pressure of 1.5 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 and maintained at a total pressure of 2.0 MPa and maintained at 70 ° C.
The average gas composition of the polymerization in the second step was C2: 80.1%. After 50 minutes, the unreacted ethylene / propylene mixed gas was purged to terminate the polymerization, and 174 g of a polymer (LCB-2) was obtained.
This sample was melt-kneaded in the same manner as in the examples and evaluated for physical properties. The value of strain hardening degree λmax of this sample is 2.5, and it is considered that a copolymer having a branched structure is formed.
The evaluation results of the polymer sample obtained are shown in Table 1.

なお、後述の比較例で用いられる市販の高溶融張力ポリプロピレンのＰＦ８１４についてもその評価結果を表１に示す。

Table 1 shows the evaluation results of PF814, which is a commercially available high melt tension polypropylene used in Comparative Examples described later.

[Example 1]
LCB-1 as a propylene polymer, and Kraton G1651 manufactured by Kraton Polymers Group as a hydrogenated product of a styrene / conjugated diene block copolymer (density is 0.91 g / cm ³ , styrene content is 32% by weight, viscosity by BMS0380 method) 1.5 Pa · s of styrene / butylene / styrene copolymer hydrogenated product (SEBS)) and blended in the proportions shown in Table 2, mixed with a mixer, and then melt-kneaded with a twin screw extruder. The strand was extruded, cooled, cut and granulated at an extrusion temperature of 200 ° C. to obtain a pellet-shaped composition. The evaluation results are shown in Table 2.

[Example 2]
As a crystalline polypropylene, Novatec EC9 (MFR 0.5 g / 10 min, melting point 161 ° C., λmax 1.0 ethylene / propylene block copolymer) manufactured by Nippon Polypro, LCB-1 as a propylene polymer, and styrene / conjugated diene Clayton G1651 (density 0.91 g / cm ³ , styrene content 32% by weight, viscosity 1.5 Pa · s by BMS0380 method) as a hydrogenated block copolymer Evaluation was performed in the same manner as in Example 1 except that the blended hydrogenated product (SEBS) was used in the ratio shown in Table 2. The evaluation results are shown in Table 2.

[Example 3]
EC9 and LCB-1, as a thermoplastic resin (C), Novatec HB332R made by Nippon Polyethylene (MFR 0.5 g / 10 min, high density polyethylene having a density of 0.952 g / cm ³ ) and Dow Chemical Engage 8150 (MFR 1.0 g) / 10 minutes, an ethylene / 1-octene copolymer having a density of 0.868 g / cm ³ and a Mooney viscosity of 33), and evaluated in the same manner as in Example 1 except that the blending ratio is as shown in Table 2. Went. The evaluation results are shown in Table 2.

[Example 4]
Evaluation was performed in the same manner as in Example 1 except that EC9, LCB-1, and Engage 8150 were used and the blending ratio was as shown in Table 2. The evaluation results are shown in Table 2.

[Example 5]
As a crystalline polypropylene, Novatec EC9 (MFR 0.5 g / 10 min, melting point 161 ° C., λmax 1.0 ethylene / propylene block copolymer) manufactured by Nippon Polypro, LCB-1 as a propylene polymer, and styrene / conjugated diene Clayton G1651 as a hydrogenated block copolymer, and talc as an inorganic filler (specific surface area 44,000 cm ² / g, average particle size 1.6 μm, particle size 10 μm or more component 0.5 wt%, MgO component) 33.1% by weight, SiO ₂ component 62.5% by weight, and other 0.45% by weight) in the proportions shown in Table 2, mixed uniformly with a mixer, and then melt-kneaded with a twin-screw extruder. The strand was extruded, cooled and cut at an extrusion temperature of 200 ° C. and granulated to obtain a pellet-shaped composition. The obtained pellets were evaluated by various evaluation methods. The evaluation results are shown in Table 2.

[Comparative Example 1]
Compounded by using Novatec BC6 (MFR 2.7 g / 10 min, melting point 163 ° C., λmax 1.0 propylene block copolymer) manufactured by Nippon Polypro as the crystalline polypropylene, LCB-1 and HB332R as the propylene-based polymer Evaluation was performed in the same manner as in Example 1 except that the ratio was as shown in Table 2. The evaluation results are shown in Table 2.

[Comparative Example 2]
Evaluation was performed in the same manner as in Example 4 except that PF814 manufactured by Basel Co., Ltd., which is commercially available as high melt tension polypropylene, was used as the propylene polymer. The evaluation results are shown in Table 2. PF814 is a propylene homopolymer introduced with a long-chain branched structure subjected to electron beam treatment.

[Comparative Example 3]
Evaluation was performed in the same manner as in Example 4 except that LCB-2 was used as the propylene polymer. The evaluation results are shown in Table 2.

[Comparative Example 4]
As a crystalline polypropylene, Novatec EC9 manufactured by Nippon Polypro, PF814 as a propylene polymer, Engage 8150 as an ethylene / α-olefin copolymer rubber, and talc as an inorganic filler (specific surface area 44,000 cm ² / g, average) Table 2 using a particle size of 1.6 μm, a component having a particle size of 10 μm or more 0.5% by weight, a MgO component 33.1% by weight, a SiO ₂ component 62.5% by weight, and other 0.45% by weight) After blending at the indicated ratio and uniformly mixing with a mixer, the mixture was melt-kneaded with a twin-screw extruder, extruded at an extrusion temperature of 200 ° C, cooled and granulated to obtain a pellet-like composition. The obtained pellets were evaluated by various evaluation methods. The evaluation results are shown in Table 2.

[Comparative Example 5]
Evaluation was performed in the same manner as in Example 1 except that EC9 and LCB-1 were used without using the thermoplastic resin (C), and the blending ratio was as shown in Table 2. The evaluation results are shown in Table 2.

[Comparative Example 6]
Evaluation was performed in the same manner as in Example 1 except that the propylene polymer (B) was not used, EC9 and G1651 were used, and the blending ratio was as shown in Table 2. The evaluation results are shown in Table 2.

  As is clear from Table 2, all of the propylene-based resin compositions having the compositions shown in Examples 1 to 5 that satisfy the respective requirements in the essential constituent elements of the present invention are draw-down resistance, physical property balance, and surface smoothness. It is remarkably improved in all properties and thermal stability, and has suitable performance for automobile exterior parts such as bumpers. On the other hand, the propylene-based resin composition using crystalline polypropylene having a high MFR shown in Comparative Example 1 has a low melt tension and inferior drawdown, and propylene using the conventional high melt tension polypropylene shown in Comparative Examples 2 and 4 The propylene resin composition using the long-chain branched propylene polymer having a high MFR shown in Comparative Example 3 is inferior in thermal stability (returnability), and the melt tension is lowered and the drawdown property is reduced. The propylene-based resin composition not using Component C shown in Comparative Example 5 has a low melt tension, and the propylene-based resin composition not using Component B shown in Comparative Example 6 has a low flexural modulus. .

  From the results of the above examples and comparative examples, the rationality and significance of the configuration of the present invention and the requirements are demonstrated, and the superiority of the present invention over the prior art is also clarified.

  The propylene-based resin composition of the present invention has good melt processing such as rigidity, impact resistance, and drawdown resistance and has improved thermal stability and excellent recyclability, particularly drawdown resistance during hollow molding, Since the surface smoothness, thermal stability, and recyclability of the molded product are improved, it becomes possible to obtain a large and complex hollow molded product by extrusion molding or blow molding using the resin composition, Since it is suitable for automobile exterior parts such as bumpers, it can be used greatly in industry.

It is a figure which shows an example of the TEM observation result of the propylene polymer (B) which concerns on this invention. It is a figure which shows an example of the TEM observation result of the propylene polymer (B) which concerns on this invention. It is a figure which shows an example of the TEM observation result of a normal propylene polymer. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer. It is a figure of explanation of the base line and section of a chromatogram in GPC

Claims (7)

The melt flow rate [230 ° C., 21.18 N load] is 0 to 79% by weight of crystalline polypropylene (A) of 0.05 to 2 g / 10 min, and at 25 ° C. satisfying the following requirements (α1) to (α5). It is composed of a component (β) insoluble in p-xylene and a component (β) soluble in p-xylene at 25 ° C. that satisfies the following requirements (β1) to (β3), and the following requirements (i) to ( propylene polymer (B) satisfying iv) 20 to 99% by weight, ethylene / α having a styrene / conjugated diene block copolymer hydrogenated product (c1) and Mooney viscosity [ML1 + 4 (121 ° C.)] of 5 or more -Olefin copolymer rubber (c2) and an ethylene polymer resin (c3) having a melt flow rate [230 ° C, 21.18N load] of 0.3 to 2 g / 10 min and a density of 0.920 g / cm ² or more. ) Without even propylene resin composition characterized by comprising a thermoplastic resin (C) 1 to 50 wt% of one.
(Α1) 20 to 95% by weight relative to the total amount of propylene polymer (B) (α2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Α3) Isotactic triad fraction (mm) measured by 13C-NMR is 93% or more,
(Α4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(Α5) Contains a propylene unit and an ethylene unit or an α-olefin unit.
(Β1) 5 to 80% by weight based on the total amount of the propylene-based polymer (B),
(Β2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Β3) Contains a propylene unit, an ethylene unit and / or an α-olefin unit.
(I) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(Ii) The component insoluble in hot p-xylene is 0.3% by weight or less,
(Iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more.
(Iv) Melt flow rate [230 degreeC, 21.18N load] is 0.05-20 g / 10min.   The propylene-based resin composition according to claim 1, wherein the component (β) further has (β4) a strain hardening degree (λmax) of 2.0 or more in the measurement of elongational viscosity.   The propylene-based resin composition according to claim 1 or 2, wherein the propylene-based polymer component (B) has a branched structure having a crystalline propylene polymer segment in the side chain and an amorphous propylene copolymer segment in the main chain. object.   The component (α) has a branched structure having a crystalline propylene polymer segment in a side chain and an amorphous propylene copolymer segment in a main chain. The propylene-based resin composition described in 1.   The propylene-based resin composition according to any one of claims 1 to 4, wherein the component (α) contains an ethylene unit and has an ethylene content of 0.1 to 10% by weight. object.   The said component ((beta)) contains an ethylene unit, Comprising: The ethylene content is 10 to 60 weight%, The propylene-type resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   A blow molded article comprising the propylene-based resin composition according to any one of claims 1 to 6.

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