JP2009263558A - Polypropylene-based blow-molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based blow-molded article excellent in impact resistance and in the uniformity of thickness. <P>SOLUTION: The polypropylene-based blow-molded article, and the like, produced by blow-molding a propylenic resin composition comprising a propylenic polymer (X) which comprises an insoluble component (A) and a soluble component (B) in p-xylene at 25°C, and has (i) a weight-average molecular weight (Mw) of 100,000-1,000,000 measured by GPC, (ii) a component insoluble in hot p-xylene of ≤0.3 wt.%, (iii) a degree of strain hardening (λmax) of ≥2.0 in measurement of elongational viscosity, and (iv) an MFR (230°C, 2.16 kg load) of 0.5 to 20 g/10 min. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polypropylene-based blow-molded product, and more particularly, to a polypropylene-based blow-molded product having particularly excellent thickness uniformity and impact resistance.

Conventionally, polyolefin resins such as polyethylene and polypropylene have been widely used as resin-made blow molded articles. In particular, when high rigidity and high impact strength are required, a propylene-ethylene block copolymer is preferably used.
Since the propylene-ethylene block copolymer has a lower impact strength than polyethylene, it is necessary to improve impact strength by adding low density polyethylene or a rubber component (see, for example, Patent Documents 1 to 3). .
However, since this reduces the rigidity, measures such as increasing the thickness of the molded body are required.

In recent years, blow molded products are often required to have a more complicated shape due to an increase in design and use range, but conventional products have poor melt ductility and drawdown properties. Therefore, it is difficult to obtain a good blow molded article. In particular, a large part such as a corner is thinned, and there is a problem that it is difficult to obtain a uniform and high-quality molded product.
Further, as a method for improving the uniformity of the thickness, a method of adding a specific polyethylene has been proposed (see Patent Document 4), but the current situation is that it does not reach a satisfactory level.
JP-A-10-158441 JP 2000-7853 A JP 2000-239480 A Japanese Patent Laid-Open No. 2002-187997

  An object of the present invention is to provide a polypropylene-based blow-molded article excellent in thickness uniformity and impact resistance in view of the above problems of the prior art.

  As a result of intensive studies to solve the above problems, the present inventors have used a propylene-based resin composition comprising a specific propylene-based polymer (X), so that the thickness uniformity and impact resistance are improved. It was found that a polypropylene-based blow molded article excellent in the above can be obtained, and the present invention has been completed.

That is, according to 1st invention of this invention, it is comprised from the component (A) which becomes insoluble in p-xylene at the following 25 degreeC, and the component (B) which melt | dissolves in p-xylene at 25 degreeC, and ( 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, and (iii) in the measurement of elongational viscosity. Propylene-based resin comprising a propylene-based polymer (X) having a strain hardening degree (λmax) of 2.0 or more and (iv) MFR (230 ° C., 2.16 kg load) of 0.5 to 20 g / 10 min. A polypropylene-based blow-molded product obtained by molding the composition by blow molding is provided.
Component (A): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (A1) to (A5).
(A1) It is 20 to 95 weight% with respect to the polymer (X) whole quantity.
(A2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(A3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 93% or more.
(A4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(A5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (B): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (B1) to (B3).
(B1) 5 to 80% by weight based on the total amount of the polymer (X).
(B2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(B3) Contains propylene units, ethylene units and / or α-olefin units.

According to the second invention of the present invention, in the first invention, the component (B) of the propylene-based polymer (X) further has (B4) a strain hardening degree (λmax) of 2. There is provided a polypropylene-based blow-molded product characterized by having a requirement of being 0 or more.
According to the third invention of the present invention, in the first invention, the propylene polymer (X) has a crystalline propylene polymer segment as a side chain and an amorphous propylene copolymer segment as a main chain. A polypropylene-based blow-molded product is provided which is composed of a polymer having a branched structure.
Furthermore, according to the fourth invention of the present invention, in the first invention, the component (A) of the propylene-based polymer (X) has a crystalline propylene polymer segment as a side chain, and an amorphous propylene copolymer segment. A polypropylene-based blow-molded product is provided, which is composed of a polymer having a branched structure having a main chain as a main chain.

According to the fifth invention of the present invention, in the first invention, the component (A) of the propylene polymer (X) contains an ethylene unit and has an ethylene content of 0.1 to 10. A polypropylene-based blow-molded product characterized in that it is wt% is provided.
Furthermore, according to the sixth invention of the present invention, in the first invention, the component (B) of the propylene-based polymer (X) contains an ethylene unit and has an ethylene content of 10 to 60% by weight. A polypropylene-based blow molded article is provided.

According to a seventh invention of the present invention, in any one of the first to sixth inventions, the propylene-based resin composition comprises 10 to 95% by weight of a propylene-based polymer (X) and a propylene-based polymer (Y And a polypropylene-based blow-molded product comprising a polymer mixture comprising 5 to 90% by weight.
According to an eighth aspect of the present invention, there is provided a polypropylene blow molded article characterized in that in any one of the first to seventh aspects, the parison is 1 m or more.
Furthermore, according to the ninth invention of the present invention, there is provided a polypropylene-based blow molded article characterized by having at least one barrier resin layer in any one of the first to eighth inventions.

As described above, the present invention relates to a polypropylene-based blow molded product obtained by a blow molding method, and preferred embodiments thereof include the following.
(1) In the first invention, the propylene-based resin composition includes a polymer mixture composed of 10 to 100% by weight of the propylene polymer (X) and 0 to 90% by weight of the propylene-based polymer (Y). A polypropylene-based blow molded article characterized by the above.
(2) In any one of the above inventions, the propylene-based resin composition is 0.01 to 0.5 parts by weight of the nucleating agent with respect to 100 parts by weight of the polymer mixture containing the propylene-based polymer (X). A polypropylene-based blow-molded article characterized by being added.
(3) In any one of the above inventions, the propylene polymer (Y) is a propylene / α-olefin block copolymer in which the α-olefin is ethylene or an α-olefin having 4 to 18 carbon atoms. A polypropylene blow molded article characterized by

  Since the polypropylene blow molded article of the present invention is formed by blow molding a propylene resin composition containing a specific propylene polymer (X), the thickness uniformity and impact resistance are improved. It has the remarkable effect of being excellent. Therefore, the polypropylene blow molded article of the present invention can be suitably used for applications such as general small containers such as food containers and detergent containers, and large parts such as automobile bumpers, construction equipment, agricultural machinery roofs, bonnets, and pallets. it can.

The polypropylene-based blow molded article of the present invention comprises the following component (A) that is insoluble in p-xylene at 25 ° C. and component (B) that is soluble in p-xylene at 25 ° C., and (i) GPC The weight average molecular weight (Mw) measured in (100) is 100,000 to 1,000,000, (ii) the component insoluble in hot p-xylene is 0.3% by weight or less, and (iii) the strain hardening degree in the measurement of elongational viscosity. A propylene-based resin composition comprising a propylene-based polymer (X) having (λmax) of 2.0 or more and (iv) MFR (230 ° C., 2.16 kg load) of 0.5 to 20 g / 10 min. , Formed by blow molding.
Component (A): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (A1) to (A5).
(A1) It is 20 to 95 weight% with respect to the polymer (X) whole quantity.
(A2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(A3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 93% or more.
(A4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(A5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (B): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (B1) to (B3).
(B1) 5 to 80% by weight based on the total amount of the polymer (X).
(B2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(B3) Contains propylene units, ethylene units and / or α-olefin units.

Hereinafter, the components of the propylene-based resin composition, the production of the propylene-based resin composition, the polypropylene-based blow molded article, and the like will be described in detail.
I. Components of propylene-based resin composition Propylene polymer (X)
The propylene-based polymer (X) constituting the propylene-based resin composition used in the polypropylene blow-molded product of the present invention is composed of a component (A) that is insoluble in p-xylene at 25 ° C and p-xylene at 25 ° C. (I) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000, and (ii) 0.3 weight of a component insoluble in hot p-xylene. (Iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more, and (iv) MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g / 10 min. is there.

  The propylene polymer (X) includes a crystalline propylene polymer component and a propylene-ethylene containing a copolymer in which a crystalline propylene polymer segment and a part of an amorphous propylene copolymer segment are chemically bonded. It is a propylene-ethylene copolymer component obtained by sequentially producing a random copolymer component by a multistage polymerization method.

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.
At this time, a part of the crystalline propylene polymer produced in the first stage is present in a state in which the reaction is terminated in the state of the terminal vinyl group. As a macromonomer, the crystalline propylene polymer is involved in the second stage polymerization, the non-crystalline 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 a certain branched structure is formed.

  The present inventors consider that the factor that the propylene-based copolymer (X) according to the present invention exhibits good thickness uniformity 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 adopt a phase separation structure on the order of level, and such a fine phase separation structure significantly improves the thickness uniformity. Actually, in the electron micrographs (FIGS. 3 and 4) of the propylene-based polymer (X) (copolymer having a branched structure) according to the present invention, ordinary resins (those having no branched structure (FIG. 5)) In comparison with the above, a very fine dispersion structure of rubber domains is seen, which supports the above inference.

  The propylene polymer (X) is 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. Is included. In addition to propylene and ethylene, the component constituting the main chain may contain other unsaturated compounds, for example, α-olefins such as 1-butene, as long as the essence of the present invention is not significantly impaired. 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. Good.

As one of the techniques for determining whether or not there is a graft copolymer in which the propylene-ethylene random copolymer component as described above is a main chain and the crystalline propylene polymer component is a side chain, It is effective to use the strain hardening degree (λmax) obtained from the measurement of the extensional 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 the propylene polymer (X) according to the present invention, a terminal propylene polymer of a vinyl group is involved in the polymerization as a macromonomer during the production of the first crystalline propylene polymer, and a branched propylene polymer is formed. To do. Therefore, this degree of strain hardening is an index of the amount of terminal vinyl propylene polymer produced, and is preferably 2.0 or more.
Here, as to 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, details of the measuring method and the measuring instrument are disclosed in the publicly known document: Polymer. 42 (2001) 8663, and preferable measuring methods and measuring instruments include the following.

Measuring method 1:
Device: 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: An extruded strand is prepared at a speed of 10 to 50 mm / min using an orifice having 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. 2 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The elongational viscosity and strain hardening degree calculated from the measuring method 1 and the measuring method 2 are, in principle, for measuring the inherent extensional viscosity and strain hardening degree of the substance and exhibit the same value. Therefore, either measurement method 1 or measurement method 2 may be used.

However, 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 the measuring method 1, when measuring a relatively high molecular weight (MFR <1), the measurement sample is contracted and deformed non-uniformly, 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, the length of branching is preferably entangled molecular weight (Me) of 7000 or more, and the degree of strain hardening is said to increase as the length of branching increases.

The propylene polymer (X) according to the present invention is separated into a crystalline component and an amorphous component, and the amount of the component (B) dissolved in p-xylene at 25 ° C. is based on the total amount of the propylene polymer (X). 5 to 80% by weight and the amount of the component (A) insoluble in p-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 removes the remaining p-xylene in the same manner and makes it a component insoluble in xylene (CXIS) at 25 ° C.

As described above, the propylene polymer (X) is composed of a crystalline component (A) and an amorphous component (B), and a part of each component is a propylene-ethylene random copolymer segment. Is a main chain and includes a copolymer having a branched structure in which the crystalline propylene polymer segment is a side chain, analytically, the following characteristics (i) to (iv), (A1) to (A5) ), (B1) to (B3).
(I): The weight average molecular weight (Mw) measured by GPC of the propylene polymer (X) is 100,000 to 1,000,000.
(Ii): The amount of components insoluble in hot paraxylene of the propylene polymer (X) is 0.3% by weight or less with respect to the total amount of the propylene polymer (X).
(Iii): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) is 2.0 or more.
(Iv): The MFR of the propylene-based polymer (X) is 0.5 to 20 g / 10 minutes.
(A1): The amount of component (A) is 20 to 95% by weight with respect to the total amount of propylene polymer (X).
(A2): The weight average molecular weight (Mw) measured by GPC of a component (A) is 100,000-1 million.
(A3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (A) is 93% or more.
(A4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (A) is 2.0 or more.
(A5): Component (A) contains a propylene unit and an ethylene unit or an α-olefin unit.
(B1): The amount of component (B) is 5 to 80% by weight based on the total amount of polymer (X).
(B2): The weight average molecular weight (Mw) measured by GPC of a component (B) is 100,000-1 million.
(B3) Component (B) contains a propylene unit, an ethylene unit and / or an α-olefin unit.

Hereinafter, each item will be described sequentially.
(I): The weight average molecular weight (Mw) measured by GPC of the propylene polymer (X) is 100,000 to 1,000,000.
As the propylene polymer (X), 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 propylene polymer (X) is in the range of 100,000 to 1,000,000. When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.
The weight average molecular weight (Mw) measured by GPC of the propylene-based polymer (X) is controlled by adjusting the temperature and monomer pressure, which are the polymerization conditions of the propylene-based polymer (X), or by propylene polymerizing a chain transfer agent such as hydrogen. Adjustments can be made easily by controlling the amount of hydrogen added at times.
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 amount of the component insoluble in the hot p-xylene of the propylene-based polymer (X) is 0.3% by weight or less based on the total amount of the polymer (X). If it exceeds 0.3% by weight, there is a risk that the molded product will be crushed and the appearance may be deteriorated.
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.
In a separable flask made of glass with a stirrer, 500 mg of a polymer is placed 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 a paraxylene insoluble part. The gel fraction (% by weight) defined as the p-xylene insoluble part was calculated by the following formula.
Gel fraction = [(residual amount in mesh g) / (prepared sample amount g)] × 100

Moreover, in order to have few gels or no gels 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 integral value in the curve is 90% by GPC is 2,000,000 or less.
Here, M (90) is a molecular weight at which the integral value in the curve is 90% by GPC measured by the GPC measuring apparatus and conditions described above. In the present invention, M (90) is 2,000,000 or less. It is a feature. When M (90) exceeds 2,000,000, the high molecular weight component is excessively increased, and a gel is generated or melt processability is deteriorated. Therefore, M (90) is 2,000,000 or less, preferably 1,500,000 or less, and more preferably 1,000,000.
The amount of components insoluble in hot p-xylene can be controlled by adjusting the temperature and monomer pressure, which are the polymerization conditions of the propylene-based polymer (X), or by controlling the amount of hydrogen added to add a chain transfer agent such as hydrogen during propylene polymerization. Adjustment can be easily performed.

(Iii): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) is 2.0 or more.
The physical significance of the strain hardening degree is as described above. If this value is large, the uneven thickness can be reduced when blow molding is performed. Therefore, this strain hardening degree needs to be 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. 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.
The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) is the selection of the metallocene complex described later, the combination thereof, and the amount thereof used in the polymerization of the propylene-based polymer (X). Adjustments can be made by controlling the ratio and prepolymerization conditions. That is, one of the two types of metallocene complexes is selected so as to easily generate a macromer, and the other is selected so that the macromer can be easily incorporated into the polymer and can generate a high molecular weight polymer. Furthermore, by performing prepolymerization, it can be adjusted by a method of uniformly distributing long chain branches among polymer particles.

(Iv): The MFR of the propylene-based polymer (X) is 0.5 to 20 g / 10 minutes.
The melt flow rate (MFR) of the propylene polymer (X) is 0.5 to 20 g / 10 minutes, and if the MFR is less than 0.5 g / 10 minutes, the fluidity is lowered and the rigidity is also lowered. . On the other hand, when the MFR exceeds 20 g / 10 minutes, the melt processability decreases. Moreover, within this range, it is preferably 0.5 to 15 g / 10 minutes, more preferably 2 to 10 g / 10 minutes, and particularly preferably 1 to 5 g / 10 minutes.
The melt flow rate (MFR) of the propylene polymer (X) is a hydrogen that adjusts the temperature and the monomer pressure, which are the polymerization conditions of the propylene polymer (X), or adds a chain transfer agent such as hydrogen during propylene polymerization. Adjustment can be easily performed by controlling the amount of addition.
Here, MFR is a value measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N (2.16 kg).

(A1): The amount of component (A) is 20 to 95% by weight with respect to the total amount of propylene polymer (X).
This rule is a range with respect to the total amount of the propylene-based polymer (X) of the component (A), and those in this range are used from the balance of rigidity and impact resistance.

(A2): The weight average molecular weight (Mw) measured by GPC of a component (A) is 100,000-1 million.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and the crystalline component (A) in the propylene polymer (X) has a weight average molecular weight of 100,000 to Those in the range of 1 million are used.
When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.
The weight average molecular weight (Mw) can be easily adjusted by adjusting the temperature and the monomer pressure, which are the polymerization conditions of the propylene polymer (X), or by controlling the amount of hydrogen added during the propylene polymerization. Adjustments can be made.

(A3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (A) is 93% or more.
The crystalline component (A) of the propylene polymer (X) according to the present invention has a stereoregularity in which the mm fraction of propylene unit three-chains obtained by ¹³ C-NMR is 93% or more.
The mm fraction is a 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. If the mm fraction of the crystalline component (A) is smaller than this value, the mechanical properties such as the elastic modulus, rigidity, heat resistance and strength of the molded article are lowered. Accordingly, the mm fraction is preferably 95% or more, and more preferably 96% or more.
The isotactic triad fraction (mm) measured by ¹³ C-NMR of the propylene polymer (X) can be adjusted by the selection of the metallocene complex described later, the polymerization temperature and the polymerization pressure.

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 at the center 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.
Spectra assignment is made according to the method described in detail in Japanese Patent Application No. 2006-311249, with reference to Macromolecules, (1975) 8 pp. 687, Polymer, 30 pages, 1350 (1989). Do.

(A4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (A) is 2.0 or more. Preferably it is 3.0 or more, More preferably, it is 4.0 or more. If it is less than 2.0, the thickness uniformity of the molded product may be impaired.
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.
The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) is the selection of the metallocene complex described later, the combination thereof, and the amount thereof used in the polymerization of the propylene-based polymer (X). Adjustments can be made by controlling the ratio and prepolymerization conditions. That is, one of the two types of metallocene complexes is selected so as to easily generate a macromer, and the other is selected so that the macromer can be easily incorporated into the polymer and can generate a high molecular weight polymer. Furthermore, by performing prepolymerization, it can be adjusted by a method of uniformly distributing long chain branches among polymer particles.

In addition, the propylene polymer (X) according to the present invention satisfies (A5) in addition to the above (A1) to (A4).
(A5): Component (A) contains a propylene unit and an ethylene unit or an α-olefin unit.
As a unit constituting the crystalline component (A), it is necessary that propylene is arranged in an isotactic manner and has crystallinity. Further, ethylene or α-olefin may be contained as a comonomer unit within a range where crystallinity is exhibited. When α, ω-diene units are present, gelation due to crosslinking is a concern, so it is necessary that no α, ω-diene units be included.
As a kind of comonomer, ethylene or a linear alpha olefin is preferable, More preferably, it is ethylene.
Regarding comonomer content, it can contain arbitrary quantity in the range which crystallinity expresses.

The melting point (Tm) measured by DSC, which is an index of crystallinity, is 120 ° C. or higher, preferably 150 ° C. or higher, more preferably 153 ° C. or higher. When the melting point (Tm) is 150 to 164 ° C., the heat resistance and rigidity are excellent.
The ethylene content of component (A) is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight, and still more preferably 0.3 to 5% by weight.
The ethylene unit is measured according to the method described in Macromolecules 1982 1150 using ¹³ C-NMR.

(B1): The amount of component (B) is 5 to 80% by weight based on the total amount of polymer (X).
This regulation is a range with respect to the total amount of the propylene polymer (X) of the component (B), and those in this range are used from the balance of rigidity and impact resistance.

(B2): The weight average molecular weight (Mw) measured by GPC of a component (B) is 100,000-1 million.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and the amorphous component (B) in the propylene polymer (X) has a weight average molecular weight of 100,000. Those in the range of ~ 1 million are used.
When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.
The weight average molecular weight (Mw) can be easily adjusted by adjusting the temperature and the monomer pressure, which are the polymerization conditions of the propylene polymer (X), or by controlling the amount of hydrogen added during the propylene polymerization. Adjustments can be made.

(B3): Component (B) contains a propylene unit, an ethylene unit and / or an α-olefin unit.
As a unit constituting the amorphous component (B), it is necessary that propylene and ethylene or α-olefin are copolymerized. Moreover, since there exists a concern about the gelatinization by bridge | crosslinking when there exists an alpha, omega-diene unit, 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 to 60% by weight. From the viewpoint of improving impact resistance, 40 to 60% by weight is particularly preferable.

(B4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (B) is 2.0 or more.
As described above, if the value of the strain hardening degree (λmax) is large, uneven thickness can be hardly generated when blow molding is performed. Therefore, when using for blow molding, 2.0 or more are preferable and 2.0-20 are still more preferable.
The strain hardening degree (λmax) in the measurement of elongational viscosity controls the selection and combination of the metallocene complexes described below used in the polymerization of the propylene-based polymer (X), the amount ratio, and prepolymerization conditions. By doing so, adjustment can be performed. That is, one of the two types of metallocene complexes is selected so as to easily generate a macromer, and the other is selected so that the macromer can be easily incorporated into the polymer and can generate a high molecular weight polymer. Furthermore, by performing prepolymerization, it can be adjusted by a method of uniformly distributing long chain branches among polymer particles.

Regarding the method for producing the propylene-based polymer (X) according to the present invention, a macromer having a vinyl terminal can be produced, and a catalyst system capable of copolymerizing the macromer with propylene and ethylene may be used. It is a feature. Among them, by using a polymerization catalyst obtained by contacting the following catalyst components (a), (b) and (c),
(I) first step of polymerizing propylene alone or propylene with 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 of polymerizing α-olefin and polymerizing 10 to 70% by weight of ethylene with respect to the total monomer components;
The propylene-based polymer (X) according to the present invention can be produced with high productivity by the step having the above.

(1) Component (a):
The catalyst component (a) used for the production of the propylene polymer (X) 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. 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.
Furthermore, 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-tbutylphenyl group, 2,3-dimethylphenyl group, 3,5-ditbutylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl Group, or a phenanthryl group, more preferably a phenyl group, a 4-tbutylphenyl 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 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 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, or a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. , 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 ( alkylsilylene groups such as n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; 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)- Thienyl) -4-phenyl-indenyl) hafnium dichloride, and the like.

  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) Component (b):
Next, the catalyst component (b) is an ion-exchange layered silicate.
In the present invention, an ion-exchange layered silicate (hereinafter sometimes simply referred to as a silicate) has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and , Refers to a silicate compound in which the contained ions are exchangeable. 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 size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in component (b).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product.
In addition, in the present invention, if there is ion exchange properties before chemical treatment, the physical and chemical properties are changed by the treatment, and silicates having no ion exchange properties or layer structures are also included. Treated as an ion-exchanged layered silicate.

Specific examples of ion-exchanged layered silicates include layered silicates having a 1: 1 type structure or a 2: 1 type structure described in, for example, Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1988). Can be mentioned.
The 1: 1 type structure is basically a stack of 1: 1 layer structure in which a single-layer tetrahedral sheet and a single-layer octahedral sheet are combined as described in “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 group 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, sea chlorite, 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.

  The ion-exchange 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, for example, 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 mentioned, and particularly preferably, agitation granulation method and spray granulation method are mentioned.
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.

  The ion-exchange layered silicate of the catalyst component (b) can be used as it is without any particular treatment, but it is desirable to perform a chemical treatment. It means contacting an alkali, organic matter, etc. with an 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.

  After carrying out the chemical treatment, it is possible to remove excess treatment agent and ions eluted by the treatment, 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.

As the catalyst component (b) according to the present invention, the chemically-exchanged ion-exchange layered silicate has an Al / Si atomic ratio of 0.01 to 0.25, preferably 0.03 to 0.24. And more preferably in the range of 0.05 to 0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion. Moreover, as a method of controlling Al / Si atomic ratio in said range, the method of using a montmorillonite and performing a chemical process as an ion-exchange layered silicate before a chemical process is mentioned.
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) Component (c):
The catalyst component (c) 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 comprises the above component (a), component (b) and 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 containing 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 component (a), component (b) and component (c) used is arbitrary, but the ratio of the transition metal in component (b) to the aluminum in component (c) is the component (a). It is preferable to make it contact so that it may become 0.1-1000 (micromol): 0-100,000 (micromol) per 1g. In addition to the component (a), other types of complexes may be used for the purpose of more efficiently producing the propylene polymer (X) according to the present invention.
In this case, it is preferable to combine a metallocene compound capable of copolymerizing the terminal vinyl macromer produced by the catalyst component (a) and producing a high molecular weight polymer compared to the catalyst component (a).
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.
Further, X ²¹ and Y ²¹ are auxiliary ligands, and react with the cocatalyst of 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 are independently hydrogen, halogen groups, hydrocarbon groups 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 other types of catalyst component (a-2) are used, the catalyst component (a-2) relative to the total amount of the catalyst component (a) and the catalyst component (a-2) is used. The ratio of the amount of) is arbitrary as long as it satisfies the properties of the propylene polymer (X), 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 of contacting the component (a), the component (b) and the component (c) is arbitrary, and after contacting two of these components, the remaining one component may be contacted, The components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of the aliphatic saturated hydrocarbon and the aromatic hydrocarbon include hexane, heptane, toluene and the like. Further, as a prepolymerized monomer, propylene can be used as a solvent.

[Prepolymerization]:
As described above, the catalyst according to the present invention is preferably subjected to a pre-polymerization treatment consisting of 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. Further, the prepolymerization amount is preferably 0.01 to 100, more preferably 0.1 to 50, by weight ratio of the prepolymerized polymer to the component (b). Further, the component (c) can be added or added during the 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 the contact of the above components is also possible.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include reduced-pressure drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. May be. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

[Detailed description of polymerization method]:
As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst comprising the catalyst component (a), the component (b) and the component (c) and the monomer efficiently come into contact with each other. 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 90 ° C, and more preferably 70 to 80 ° C. The polymerization pressure is 0 to 5 MPaG, preferably 0 to 4 MPaG.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Moreover, it is preferable not to use hydrogen as a molecular weight regulator in order to suppress chain transfer by hydrogen and increase the terminal vinyl content.

[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.

  The propylene-based 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. Is 0.3% or less, (iii) the strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more, and (iv) MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g. / 10 minutes, and includes a copolymer in which a crystalline segment is grafted to an amorphous segment as a side chain. 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.

2. Propylene polymer (Y)
The propylene polymer (Y) is selectively blended in the propylene resin composition constituting the polypropylene blow molded article of the present invention. When the propylene polymer (Y) is used alone, it is difficult to obtain a polypropylene blow molded product having sufficient thickness uniformity, transparency, rigidity and impact resistance, but the propylene polymer (X) is blended. Thereby, the thickness uniformity, transparency, rigidity, and impact resistance of the obtained polypropylene-based blow molded article can be remarkably improved.
Such propylene-based polymer (Y) may be either a propylene homopolymer or a copolymer of propylene and another α-olefin, but a copolymer of propylene and α-olefin, particularly Propylene / α-olefin block copolymers are preferred.

The propylene / α-olefin block copolymer preferably used is a propylene / α-olefin copolymer obtained by sequentially producing a crystalline propylene polymer component and a propylene / α-olefin random copolymer component by a multistage polymerization method. It is a polymer component.
The α-olefin used as a comonomer is preferably ethylene or an α-olefin having 4 to 18 carbon atoms. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1 etc. can be mentioned. Moreover, as an alpha olefin, 1 type or the combination of 2 or more types may be sufficient.

(1) Properties of propylene polymer (Y) The melt flow rate (MFR) of the propylene polymer (Y) is preferably 0.1 to 5 g / 10 minutes, more preferably 0.3 to 3 g / 10 minutes. 0.5-2 g / 10 min is particularly preferred. When the MFR is less than 0.1 g / 10 min, the fluidity is lowered and the rigidity is also lowered. On the other hand, if the MFR exceeds 5 g / 10 min, the melt processability is lowered and the drawdown is increased during molding, which is not preferable.
Here, MFR is a value measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N (2.16 kg).

(2) Polymerization method of propylene-based polymer (Y) The propylene-based polymer (Y) uses a so-called Ziegler-Natta catalyst or metallocene catalyst containing magnesium, titanium, halogen, and an electron donor as essential components. Thus, it can be produced by a known method.
In the present invention, commercially available products can be used as the crystalline propylene / α-olefin block copolymer, and examples thereof include Novatec PP and Newcon manufactured by Nippon Polypro Co., Ltd.
The propylene polymer (Y) may be used as one kind or a mixture of two or more kinds of polymers.

(3) Blending ratio of propylene-based polymer (X) and propylene-based polymer (Y) In the propylene-based resin composition used in the polypropylene-based blow-molded product of the present invention, the propylene-based polymer (X) and the propylene-based polymer The blending ratio of the polymer (Y) is 10% by weight or more (10 to 100% by weight) of the propylene polymer (X), and 90% by weight or less (0 to 90% by weight) of the propylene polymer (Y). Desirably, the propylene polymer (X) is 10 wt% or more and 95 wt% or less (10 to 95 wt%), and the propylene polymer (Y) is 5 wt% or more and 90 wt% or less (5 to 5 wt%). 90% by weight), preferably a polymer mixture in which the propylene polymer (X) is 20% by weight or more and the propylene polymer (Y) is 80% by weight or less. More preferred Particularly preferred is a polymer mixture in which the propylene polymer (X) is 50% by weight or more and the propylene polymer (Y) is 50% by weight or less. When the blending amount of the propylene polymer (X) is less than 10% by weight, the improvement effect on the propylene polymer (Y) is poor.

4). Other compounding agents In addition to the propylene polymer (X) and the propylene polymer (Y), the propylene resin composition used in the polypropylene blow molded article of the present invention is generally known for use in polyolefins. Various additives such as a nucleating agent, an antioxidant, a neutralizing agent, a light stabilizer, an ultraviolet absorber, an inorganic filler, an antiblocking agent, a lubricant, an antistatic agent and a metal deactivator are used for the purpose of the present invention. It can mix | blend in the range which is not impaired.

As nucleating agents, sorbitols such as sodium 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4-di (p-methylbenzylidene) sorbitol Compound, hydroxy-di (aluminum t-butylbenzoate, 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid and aliphatic monocarboxylic acid lithium salt having 8 to 20 carbon atoms (Asahi An example is Denka Co., Ltd. product name NA21).
As a compounding quantity of a nucleating agent, a well-known compounding quantity can be used, About 0.01-0.5 weight part of nucleating agents can be normally mix | blended with respect to 100 weight part of polymer mixtures.
Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants, and examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate, Examples of the light stabilizer and the ultraviolet absorber include hindered amines, nickel complex compounds, benzotriazoles, and benzophenones.
Examples of inorganic fillers and anti-blocking agents include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, and examples of lubricants include higher fatty acid amides such as stearic acid amide. it can.
Furthermore, examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester, and examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, and oxamides. it can.

II. Preparation method of propylene-based resin composition As a preparation method of the propylene-based resin composition used in the present invention, the propylene-based polymer (X) in the form of powder or pellets, and a propylene-based polymer used as necessary The method of mixing (Y) and other compounding agents with a dry blend, a Henschel mixer, etc. can be mentioned.

III. Polypropylene blow molded article The polypropylene blow molded article of the present invention can be obtained by blow molding the propylene resin composition using a known blow molding machine.
In order to mold a large blow molded article that can further exert the effect of the present invention, a general direct blow molding method in which a cylindrical molten resin (parison) is extruded and then closed by a mold, is inflated by air pressure, and is cooled and solidified. preferable.

  In particular, in a large blow molded product having a product size of 1 m or more, the extruded molten resin is partially stretched due to its own weight, resulting in non-uniform wall thickness or cutting and dropping. Although it is easy to occur, the propylene-based resin composition has an excellent melt ductility while the extruded molten resin has high fluidity, and therefore the parison is 1 m or more (product size is 1 m or more). Even in large-scale blow molding, the above-mentioned molding defects are unlikely to occur, so that a high-quality polypropylene blow molded article that has never been obtained can be obtained.

As molding conditions for blow molding, it is preferable that the molding temperature is 120 to 250 ° C., the blowing pressure is ^{2 to} 10 kg / cm ² , and the blow ratio is 1.2 to 5.0.

Moreover, in this invention, even if it is a polypropylene-type blow molded object by single layer extrusion, the polypropylene-type multilayer blow molded object by multilayer extrusion molding with various resin may be sufficient.
In the case of a polypropylene-based multilayer blow molded article, the propylene-based resin composition can be used for any layer such as an inner layer, an intermediate layer, and an outer layer. A three-layer five-layer configuration of layer / propylene-based resin layer is a preferable layer configuration.

Further, in a blow molded article having a barrier layer, the propylene-based resin composition is required to have higher melting characteristics (melt flowability, melt spreadability) than a single layer. When the melting characteristics of the main propylene resin composition are poor, the molten resin extruded during parison formation draws down due to its own weight, and the upper part becomes thin and the lower part becomes thicker. The upper barrier layer of the body does not reach the minimum thickness necessary for maintaining the barrier property.
Therefore, the barrier layer of the molten resin to be extruded must be set thick, but the lower barrier layer of the resulting blow molded article becomes thicker. If the barrier layer having poor melt spreadability is thickened with respect to the propylene-based resin, the blow moldability is deteriorated, and a blow molded product with poor quality is obtained.

Examples of the resin used for the barrier layer include polyesters such as polyethylene terephthalate, polyamides such as nylon 6, nylon 66, and MX nylon, ethylene-vinyl alcohol copolymers, polyvinylidene chloride, and the like. It is possible to use multiple layers. Moreover, other resin can also be mixed within the range which does not impair the effect.
As the resin used for the adhesive resin layer, propylene-based unsaturated carboxylic acid such as maleic anhydride, acrylic acid, methacrylic acid or the like, or graft-modified polypropylene, propylene / α-olefin copolymer, etc. are used. .

IV. Use of Polypropylene Blow Molded Article The polypropylene blow molded article of the present invention is excellent in mechanical properties such as rigidity and impact resistance and has excellent thickness stability. Therefore, it is suitable not only for general small containers such as food containers and detergent containers, but also for large parts such as automobile bumpers, construction machines, agricultural machine roofs, bonnets, and pallets that have been prone to molding defects.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, the physical properties of polypropylene-based blow molded articles or their constituent components were measured and evaluated according to the following evaluation methods, and the following resins were used.

1. Evaluation method (1) Melt flow rate (MFR) [unit: g / 10 min]:
The propylene-based resin conforms to JIS K7210: 1999 “Method for testing plastics-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR)”, condition M (230 ° C., 2.16 kg load). Measured in conformity.
(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 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) Determination of ethylene content The average ethylene content in the copolymer was measured using an infrared spectrophotometer. The measurement conditions are shown below.
Equipment: Shimadzu FTIR-8300
Resolution: 4.0 cm ⁻¹
Measurement range: 4,000 to 400 cm ⁻¹
Sample adjustment: Polymer powder or pellets are adjusted to a film with a thickness of 500 μm with a heating and pressing press (temperature 190 ° C., preheating 2 minutes before pressing to 100 MPa)
Data processing:
(I) Using 760,700 cm ⁻¹ as a base point, calculate the absorbance peak area in that range (corresponding to ethylene content).
(Ii) Calculate the peak area / sample thickness.
(Iii) A calibration curve is prepared with a sample whose ethylene content has been quantified in advance by NMR, and the ethylene content is quantified by the formula [ethylene content∝peak area / sample thickness].

(7) Molecular weight distribution:
It was measured by the method described in the present specification.
(8) Impact resistance:
Ten cylindrical bottles were filled with 500 cc of water, and a sheet of 0.5 mm thickness that was pre-heat-compressed with the same material as this sample container was used for 30 seconds with a butt welder heated to about 200 ° C. for 2 seconds. The cylindrical bottle mouth was heat sealed with pressure. Next, after adjusting the state for 24 hours at a temperature of 23 ° C., the number of breaks when dropped vertically 10 times vertically from a height of 1.2 m in a low-temperature room at 23 ° C. was evaluated.
(9) Rigidity:
The cylindrical bottle was compressed from above with a compression tester at a speed of 50 mm / min, and the maximum compressive strength (buckling strength) was measured.
(10) Uneven thickness of cylindrical bottle:
At the center of the body of the cylindrical bottle (15 cm in height from the bottom), the thickness in the circumferential direction was measured with a Mitutoyo micrometer, and the difference between the maximum value and the minimum value was determined. It means that the smaller the numerical value, the more uniform the thickness of the cylindrical bottle, the smaller the uneven thickness, and the better the product.
(11) Drawdown resistance:
Using an IHI IPB10BML blow molding machine at a resin temperature of 200 ° C. When a panel having a length of 1.5 m, a width of 1.0 m, and a weight of 8.5 kg is molded, the one having a ratio of the upper wall thickness to the lower wall thickness of the molded body of 0.8 to 1.0 is regarded as good. Less than .8 or poorly formed or unmoldable was regarded as defective.

2. Materials used (1) Propylene polymer (X)
The polymers (PP-1) to (PP-6) produced in the following Production Examples 1 to 6 and a commercially available polypropylene resin (PF814) were used.

[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:
To 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 (CDCl 3}} ) Identification Results
Racemate: δ 1.12 (s, 6H), δ 2.42 (s, 6H), δ 6.06 (d, 2H), δ 6.24 (d, 2H), δ 6.78 (dd, 2H), δ 6. 97 (d, 2H), δ 6.96 (s, 2H), δ 7.25 to δ 7.64 (m, 12H).

(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, and the entire amount of the above-mentioned cake solid was added, and further 522 g of distilled water 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, 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, then washed to 1/1000 with heptane, 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 resulting 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 48.0 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 1.40.

(3) [Polymerization]
First step polymerization:
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution was added, and the internal temperature was maintained at 30 ° C. Next, 8 g of the prepolymerized catalyst (with the weight reduced from the prepolymerized polymer) was injected with argon to start polymerization, and the temperature was raised to 70 ° C. over 32 minutes, and the polymerization temperature was maintained at 70 ° C. After 1 hour, unreacted propylene was purged and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.

Second step polymerization:
To maintain the above nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, introduce 1.0 MPa in partial pressure of propylene and then 1.0 MPa in partial pressure of ethylene, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 81 mol% and 19 mol%, respectively, and the conditions of 50 ° C. and a total pressure of 2.0 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 54.1%. Two hours later, 100 ml of ethanol was introduced to stop the reaction. Unreacted ethylene / propylene mixed gas was purged to obtain 11.3 kg of polymer (PP-1).

[Production Example 2]
(1) [Polymerization]:
First step polymerization:
The same polymerization as in the first step of Production Example 1 was carried out except that 9.5 g of the prepolymerized catalyst (with the weight obtained by subtracting the prepolymerized polymer) was used.

Second step polymerization:
To maintain the above nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, introduce 0.5 MPa of propylene with a partial pressure and then 1.5 MPa with a partial pressure of propylene, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 58 mol% and 42 mol%, respectively, and the conditions of 50 ° C. and a total pressure of 2.0 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 72.9%. Two hours later, 100 ml of ethanol was introduced to stop the reaction. Unreacted ethylene / propylene mixed gas was purged to obtain 9.7 kg of polymer (PP-2).

[Production Example 3]
(1) [Synthesis of rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride]:
Synthesis was performed according to the method described in JP-A-2004-2259.

(2) [Catalyst synthesis]:
In a three-necked flask (volume: 1 L), 20 g of silica-supported MAO (product name: MAO-S manufactured by WITCO) was added, and heptane (200 mL) was added to prepare a slurry.
In another flask (volume 200 mL), heptane (85 mL) was added to rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride (0.3 mmol). Then, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 30 minutes at room temperature to react. This solution was added to a 3 L flask containing silica-supported MAO and stirred at room temperature for 30 minutes. Thereafter, 215 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After setting the internal temperature of the autoclave 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 carried out for 0.5 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 55.9 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 1.80.

(3) [Polymerization]:
First step polymerization:
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 10 liters of hydrogen (as a standard volume) and 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was maintained at 30 ° C. Next, 8 g of the prepolymerized catalyst (with the weight reduced from the prepolymerized polymer) was injected with argon to start polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the polymerization temperature was maintained at 70 ° C. After 1 hour, unreacted propylene was purged and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.

Second step polymerization:
To maintain the above nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, introduce propylene into a partial pressure of 0.3 MPa, then introduce ethylene into a partial pressure of 1.2 MPa, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 36 mol% and 64 mol%, respectively, and the conditions of 50 ° C. and a total pressure of 1.5 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 80.3%. After 3.5 hours, 100 ml of ethanol was introduced to stop the reaction. The unreacted ethylene / propylene mixed gas was purged to obtain 11.6 kg of a polymer (PP-3).

[Production Example 4]
(1) [Polymerization]
First step polymerization:
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution was added, and the internal temperature was maintained at 30 ° C. Next, 10 g of the prepolymerized catalyst synthesized in Production Example 1 (with the weight obtained by subtracting the prepolymerized polymer) was injected with argon to start the polymerization, the temperature was raised to 75 ° C. over 30 minutes, and the polymerization temperature was raised to 75 ° C. Maintained. After 1 hour, unreacted propylene was purged and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.

Second step polymerization:
In order to maintain the above-mentioned nitrogen-substituted autoclave at 70 ° C. and atmospheric pressure, introduce propylene into a partial pressure of 0.5 MPa, then introduce ethylene into a partial pressure of 1.5 MPa, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 34 mol% and 66 mol%, respectively, and the conditions of 70 ° C. and a total pressure of 2.0 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 80.1%. After 50 minutes, 100 ml of ethanol was introduced to stop the reaction. Unreacted ethylene / propylene mixed gas was purged to obtain 9.0 kg of polymer (PP-4).

[Production Example 5]
(1) [Synthesis of rac- (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride]:
The synthesis of rac- (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride was carried out in the same manner as in Example 1 of JP-A-11-240909. did.

(2) [Catalyst synthesis]:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained in Production Example 1 is added, and heptane (66 mL) is added to form a slurry. 34 mL) was added, and the mixture was stirred for 1 hour, washed with heptane to 1/1000, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (0. 135 mmol) was dissolved in toluene (38 mL) (complex solution 1).
In another flask (volume 200 mL), rac- (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride (0. 015 mmol) was dissolved in toluene (5 mL) (complex solution 2).
To a 3 L flask containing chemically treated smectite, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added, and the complex solution 1 was added, followed by the addition of the complex solution 2. Stir at room temperature for 60 minutes. Thereafter, 356 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After setting the internal temperature of the autoclave to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, propylene feed was stopped, and residual polymerization was performed at 50 ° C. for 0.5 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 27.5 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 1.75.

(3) [Polymerization]
First step polymerization:
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution was added, and the internal temperature was maintained at 30 ° C. Next, 6 g of the prepolymerized catalyst (with a weight obtained by subtracting the prepolymerized polymer) was injected with argon to start polymerization, and the temperature was raised to 75 ° C. over 35 minutes, and the polymerization temperature was maintained at 75 ° C. After 1 hour, unreacted propylene was purged and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.

Second step polymerization:
To maintain the nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, introduce propylene with a partial pressure of 0.7 MPa, then ethylene with a partial pressure of 1.3 MPa, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 67 mol% and 33 mol%, respectively, and the conditions of 50 ° C. and a total pressure of 2.0 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 65.1%. After 1 hour, 100 ml of ethanol was introduced to stop the reaction. The unreacted ethylene / propylene mixed gas was purged to obtain 9.8 kg of a polymer (PP-5).

[Production Example 6]
(1) [Polymerization]:
First step polymerization:
The same polymerization as in the first step of Production Example 5 was performed.

Second step polymerization:
To maintain the above nitrogen-substituted autoclave at 55 ° C. and atmospheric pressure, introduce propylene in a partial pressure of 0.58 MPa, then ethylene in a partial pressure of 1.42 MPa, and then maintain the gas composition of propylene and ethylene Propylene and ethylene were supplied at a ratio of 57 mol% and 43 mol%, respectively, and the conditions of 55 ° C. and a total pressure of 2.0 MPa were maintained. The average gas composition of the polymerization in the second step was C2: 70.8%. Two hours later, 100 ml of ethanol was introduced to stop the reaction. The unreacted ethylene / propylene mixed gas was purged to obtain 10.3 kg of a polymer (PP-6).

(Commercial goods)
PF814 (electron beam irradiated product):
High melt tension polypropylene (MFR = 2.5 g / 10 min) manufactured by Basel Co. was used.

Propylene polymer (Y):
EC9:
A propylene-based block copolymer (MFR = 0.5 g / 10 min) manufactured by Nippon Polypro was used.
Adhesive layer:
A polypropylene adhesive resin (Modic P604V manufactured by Mitsubishi Chemical Corporation) was used.
Barrier layer:
EVOH (Nippon Synthetic Chemical Industry Co., Ltd. Soarnol DC3203F) was used.

[Example 1]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate which is a phenolic antioxidant with respect to 100 parts by weight of the polymer (PP-1). ] Methane (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168) which is a phosphite antioxidant , Ciba Specialty Chemicals Co., Ltd.) 0.05 part by weight, and 0.05 parts by weight of calcium stearate (trade name: Calcium Stearate, manufactured by Nippon Oil & Fats Co., Ltd.) as a neutralizing agent After mixing for 3 minutes at room temperature with a mixer (Henschel mixer, trade name), the mixture was melt-kneaded with an extruder to produce polymer PP-1 pellets. Obtained.

(Cylindrical bottle)
The obtained polymer PP-1 pellet is a small direct blow molding machine JB105 manufactured by Nippon Steel Co., Ltd. having a diameter and diameter of 50 mmφ with a dalmage kneading part at the tip and a L / D22 screw and die having a crosshead structure. A polypropylene blow molded article (cylindrical bottle) having a bottle weight of 30 g and an internal capacity of 550 cc was molded under the conditions of a molding temperature of 200 ° C., a blow mold cooling temperature of 15 ° C., and a cooling time of 24 seconds.

(panel)
The obtained polymer PP-1 pellets were used in a polypropylene system having a resin temperature of 200 ° C., a length of 1.5 m, a width of 1.0 m, and a weight of 8.5 kg using an IHI IPB10BML blow molding machine. A blow molded body (panel) was molded.
The evaluation results of these polypropylene blow molded articles are shown in Table 1.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 2]
The same procedure as in Example 1 was performed except that the polymer (PP-2) was used instead of the polymer (PP-1), and a cylindrical bottle with an inner capacity of 550 cc with a bottle weight of 30 g and a weight of 8.5 kg was used. Panels were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 3]
Example except that a polymer mixture obtained by blending 80% by weight of polymer (PP-2) and 20% by weight of propylene-based resin (Y: EC9) was used instead of polymer (PP-2). In the same manner as in No. 2, a cylindrical bottle with a bottle weight of 30 g and an internal capacity of 550 cc and a panel with a weight of 8.5 kg were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 4]
Example except that a polymer mixture obtained by blending 60% by weight of polymer (PP-2) and 40% by weight of propylene resin (Y: EC9) was used instead of polymer (PP-2). In the same manner as in No. 2, a cylindrical bottle with an internal capacity of 550 cc with a bottle weight of 30 g and a panel with a weight of 8.5 kg were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 5]
Example except that a polymer mixture obtained by blending 20% by weight of polymer (PP-2) and 80% by weight of propylene resin (Y: EC9) was used instead of polymer (PP-2). In the same manner as in No. 2, a cylindrical bottle with an inner capacity of 550 cc with a bottle weight of 30 g and a panel with a weight of 8.5 kg were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 6]
The same procedure as in Example 1 was performed except that the polymer (PP-5) was used instead of the polymer (PP-1), and a cylindrical bottle with an inner capacity of 550 cc with a bottle weight of 30 g and a weight of 8.5 kg was used. Panels were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 7]
The same procedure as in Example 1 was carried out except that the polymer (PP-6) was used instead of the polymer (PP-1), a cylindrical bottle having an internal capacity of 550 cc with a bottle weight of 30 g and a weight of 8.5 kg. Panels were molded.
Table 1 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and had a uniform thickness.

[Example 8]
Instead of the polymer (PP-2), 100% by weight of the polymer (PP-2) and 20% by weight of the propylene-based resin (Y: EC9) were blended with phenol. Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) 0.05 part by weight, 0.05 part by weight of tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168, manufactured by Ciba Specialty Chemicals Co., Ltd.) which is a phosphite-based antioxidant In addition, 0.05 part by weight of calcium stearate (trade name: calcium stearate, manufactured by Nippon Oil & Fats Co., Ltd.), which is a neutralizing agent, is blended and stirred at high speed After mixing for 3 minutes at room temperature with a mixer (Henschel mixer, trade name), the mixture was melt-kneaded with an extruder to obtain pellets.

Using the obtained pellets (polymer mixture), Modic P604V (adhesive) and EVOH (Soarnol DC3203F), three screws of 50 mmφ, 40 mmφ, 40 mmφ and a three-kind five-layer die structure manufactured by Placo Corporation Polymer mixture layer / adhesive layer / EVOH layer / adhesive using a multi-layer direct blow molding machine S-50ND in a molding temperature of 200 ° C., blow mold cooling temperature of 15 ° C., and cooling time of 24 seconds. A polypropylene multilayer blow molded article (cylindrical bottle) having a three-part five-layer constitution of a layer / polymer mixture constitution and a thickness ratio of 45/3/4/3/45 with a bottle weight of 30 g and an internal capacity of 550 cc was formed.
In addition, the obtained pellets were produced using a polypropylene multilayer blow molding having a resin temperature of 200 ° C., a length of 1.5 m, a width of 1.0 m, and a weight of 8.5 kg using an IHI IPB10BML blow molding machine. A body (panel) was molded.
The evaluation results of the obtained polypropylene-based multilayer blow molded article are shown in Table 1.
The polypropylene multilayer blow molded article satisfying the constitution of the present invention was excellent in mechanical property balance and uniform in thickness.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that a propylene resin (PF814) different from the propylene polymer (X) specified in the present invention was used instead of the polymer (PP-1), and the bottle weight was 30 g. A cylindrical bottle having an internal volume of 550 cc and a panel weighing 8.5 kg were molded.
Table 2 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene-based blow molded article satisfying the constitution of the present invention was inferior in the mechanical property balance and inferior in appearance in which the surface was dotted with irregularities.

[Comparative Example 2]
Except for the propylene polymer (X) specified in the present invention and using 100% by weight of the propylene polymer (Y: EC9) specified in the present invention, the same procedure as in Example 1 was carried out, and the bottle weight was 30 g. A cylindrical bottle having a capacity of 550 cc and a panel weighing 8.5 kg were molded.
Table 2 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the constitution of the present invention was inferior in the mechanical property balance and the thickness was not uniform.

[Comparative Example 3]
The same procedure as in Example 1 was performed except that a polymer (PP-3) different from the propylene-based polymer (X) specified in the present invention was used instead of the polymer (PP-1), and the bottle weight A 30 g internal capacity 550 cc cylindrical bottle and a panel weighing 8.5 kg were molded.
Table 2 shows the evaluation results of the obtained polypropylene blow molded article.
The polypropylene blow molded article satisfying the configuration of the present invention had a non-uniform thickness.

[Comparative Example 4]
The same procedure as in Example 1 was conducted except that a polymer (PP-4) different from the propylene polymer (X) specified in the present invention was used instead of the polymer (PP-1), and the bottle weight An attempt was made to mold a 30 g cylindrical bottle with an internal capacity of 550 cc and a weight of 8.5 kg, but the drawdown was severe and could not be molded.
The evaluation results are shown in Table 2.

  The polypropylene-based blow molded article of the present invention has a remarkable effect that it has excellent thickness uniformity and impact resistance, so that it can be used for general small containers such as food containers and detergent containers, automobile bumpers, and construction machinery. It is extremely useful for applications such as agricultural machinery roofs, bonnets, large parts such as pallets.

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

Claims (9)

It is composed of the following component (A) that is insoluble in p-xylene at 25 ° C. and component (B) that is soluble in p-xylene at 25 ° C., and (i) the weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000, (ii) a component insoluble in hot p-xylene is 0.3% by weight or less, and (iii) a strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more. , (Iv) A polypropylene system obtained by molding a propylene-based resin composition containing a propylene-based polymer (X) having an MFR (230 ° C., 2.16 kg load) of 0.5 to 20 g / 10 min by blow molding. Blow molded body.
Component (A): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (A1) to (A5).
(A1) It is 20 to 95 weight% with respect to the polymer (X) whole quantity.
(A2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(A3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 93% or more.
(A4) The strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more.
(A5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (B): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (B1) to (B3).
(B1) 5 to 80% by weight based on the total amount of the polymer (X).
(B2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(B3) Contains propylene units, ethylene units and / or α-olefin units.   The component (B) of the propylene-based polymer (X) further has a requirement that (B4) the strain hardening degree (λmax) in the measurement of elongational viscosity is 2.0 or more. The polypropylene-based blow-molded article described in 1.   The propylene polymer (X) is composed of a polymer having a branched structure having a crystalline propylene polymer segment as a side chain and an amorphous propylene copolymer segment as a main chain. The polypropylene-based blow-molded article described in 1.   Component (A) of the propylene polymer (X) is composed of a polymer having a branched structure in which a crystalline propylene polymer segment is a side chain and an amorphous propylene copolymer segment is a main chain. The polypropylene-based blow molded article according to claim 1.   2. The polypropylene blow molding according to claim 1, wherein the component (A) of the propylene polymer (X) contains an ethylene unit and has an ethylene content of 0.1 to 10% by weight. body.   The polypropylene blow molded article according to claim 1, wherein the component (B) of the propylene polymer (X) contains an ethylene unit and has an ethylene content of 10 to 60% by weight.   The propylene resin composition contains a polymer mixture composed of 10 to 95% by weight of a propylene polymer (X) and 5 to 90% by weight of a propylene polymer (Y). The polypropylene-based blow molded article according to any one of -6.   The polypropylene blow molded article according to any one of claims 1 to 7, wherein the parison is 1 m or more.   The polypropylene-based blow-molded article according to any one of claims 1 to 8, comprising at least one barrier resin layer.

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