JP4990217B2 - Propylene resin composition and molded article thereof - Google Patents

Description

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

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

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

Recently, attempts have been made to improve the melt tension by modifying the molecular structure of the polypropylene resin itself. A method of irradiating the polypropylene resin with an electron beam (Patent Document 4), and converting the polypropylene resin into a peroxide. Obtained by prepolymerizing a high-molecular-weight olefin polymer in the presence of an olefin polymerization catalyst, a method of treating with a crosslinking aid (Patent Document 5), a method of copolymerizing propylene and polyene (Patent Document 6). A method of polymerizing propylene in the presence of a prepolymerization catalyst (Patent Document 7) has been proposed.
However, in the method of irradiating the polypropylene resin with an electron beam or the method of treating the polypropylene resin with a peroxide or a crosslinking aid, it is difficult to control the side reaction of higher order crosslinking, and the appearance of the gel is caused Defects and smoothness will be adversely affected. Moreover, in the method of copolymerizing propylene and polyene, the effect of improving the melt tension is not always sufficient, and there is a concern about the generation of gel. Further, in any method of polypropylene resin, there is a problem that the melt tension changes due to the thermal history.
In other words, in molding, especially hollow molding, it is customary to recycle raw materials by collecting burrs from the viewpoint of environmental issues and economics (hereinafter sometimes referred to as returns). Since the burrs that have undergone a history have a lower melt tension, even if the return rate is small, the melt processing characteristics cannot be ignored. In this way, there was a problem in returnability.
Under such circumstances, the propylene-based resin composition that solves the problems in the prior art, has good melt processing such as rigidity, impact resistance, and drawdown resistance, has improved thermal stability, and has excellent return properties There is a need for early development.
Japanese Patent Laid-Open No. 3-197542 JP-A-8-92438 Japanese Patent Laid-Open No. 7-316361 JP-A-2-298536 WO99 / 27007 International Publication Pamphlet JP-A-5-194778 JP-A-10-231394

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

  In order to solve the above-mentioned problems, the present inventors have made a novel study showing a high degree of strain hardening (λmax) and an isotactic triad fraction (mm fraction) that promotes improvement in the balance of physical properties as a result of intensive studies. When a chain-branched propylene polymer is used and a specific resin component is blended in a specific ratio, the resulting propylene resin composition has a melt processing such as rigidity, impact resistance, and drawdown resistance. Has been found to be good and the thermal stability is improved and the return property is also excellent, and the present invention has been completed.

That is, according to the first invention of the present invention, 50 to 99% by weight of the propylene polymer (A) satisfying the following requirements (i) to (vi) and hydrogenation of the styrene / conjugated diene block copolymer: Product (b1), ethylene / α-olefin copolymer rubber (b2) having a Mooney viscosity [ML1 + 4 (121 ° C.)] of 5 or more, or MFR [230 ° C., 21.18 N load] of 0.3-2 g / A propylene-based resin composition comprising 1 to 50% by weight of at least one thermoplastic resin (B) selected from ethylene polymer resin (b3) having a density of 0.920 g / cm ³ or more for 10 minutes. Is provided.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.01 g / 10 min or more and 100 g / 10 min or less.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm fraction) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.

According to the second invention of the present invention, there is provided a propylene-based resin composition according to the first invention, wherein the propylene-based polymer (A) further satisfies the following requirement (vii): Is done.
Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

According to the third invention of the present invention, in the first or second invention, the propylene polymer (A) further satisfies the following requirement (viii): Is provided.
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.

  Moreover, according to the 4th invention of this invention, the blow molded object which consists of a propylene-type resin composition which concerns on any 1st-3rd invention is provided.

  The propylene-based resin composition of the present invention is remarkably improved in draw-down resistance, physical property balance, surface smoothness and thermal stability (return property) of the molded product during hollow molding. Therefore, blow molding using this enables a large and complex hollow molded body, which is suitable for automobile exterior parts such as bumpers.

As described above, the propylene-based resin composition of the present invention may be simply referred to as a propylene-based polymer (A) that satisfies the following requirements (i) to (vi) (hereinafter simply referred to as “component (A)”). .) Ethylene / α-olefin copolymer rubber (b2) having 50 to 99% by weight, hydrogenated styrene / conjugated diene block copolymer (b1), Mooney viscosity [ML1 + 4 (121 ° C.)] of 5 or more Or at least one thermoplastic resin selected from ethylene polymer resin (b3) having an MFR of [230 ° C., 21.18 N load] of 0.3 to 2 g / 10 min and a density of 0.920 g / cm ³ or more. (B) (hereinafter sometimes simply referred to as “component (B)”) 1 to 50% by weight.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.01 to 100 g / 10 min.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4 wt% or more and less than 10 wt%.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm fraction) measured by 13C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.
Hereafter, each component of the propylene-type resin composition of this invention, manufacture of the resin composition, a molded object, etc. are demonstrated in detail.

[I] Components of propylene-based resin composition Component (A): Propylene polymer (A)
The propylene-based polymer used in the present invention has the following requirements (i) to (vi), or in addition to these, the properties and properties shown in the requirements (vii) and / or the requirements (viii): Features.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.01 to 100 g / 10 min.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4 wt% or more and less than 10 wt%.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm fraction) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.
Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.
Hereinafter, each item will be described sequentially.

I. Propylene Polymer Structure, Long-Chain Branched Structure Definition and Identification Method The propylene polymer of the present invention has excellent balance between physical properties and melt processability with controlled melt fluidity (melt stretchability) and melt tension. It is a long chain branched propylene polymer.
The propylene-based polymer of the present invention is considered that the melt properties are remarkably improved by introducing the above-mentioned long chain branching.
In general, ¹³ C-NMR is used for directly detecting and quantifying the branched structure and the number of branches. Further, ¹³ C-NMR, GPC-vis, and GPC-malls are used for detection and quantification of the number of branches and branch distribution. However, the above method has a limit of quantification. At present, rheological methods are considered to have the highest sensitivity as a method for evaluating branching. For example, measurement of flow activation energy in linear viscoelasticity measurement and strain hardening degree in elongational viscosity measurement are generally used at this stage as a method for detecting a small amount of branching.
Regarding the branched structure, the present inventors have inferred as follows in consideration of the mechanism and mechanism capable of forming the branched structure.

That is, from the active species derived from the catalyst component [A-1] used in the method for producing a propylene-based polymer, which will be described later, one end of the polymer mainly has a propenyl structure (by a special chain transfer reaction generally called β-methyl elimination). Vinyl structure) and so-called macromers are formed.
The terminal propenyl structure (vinyl structure) terminated by the β-methyl elimination reaction is shown below (reference document: Macromol. Rapid Commun. 2000, 21, 1103-1107).

This macromer can generate a higher molecular weight, and is assumed to be incorporated into the active species derived from the catalyst component [A-2] having better copolymerizability described later, and the macromer copolymerization is proceeding. Yes.
Therefore, the propylene polymer of the present invention has a specific branched structure as shown in the following structural formula (2).
In Structural Formula (2), Ca, Cb, and Cc represent methylene carbon adjacent to the branched carbon, Cbr represents the methine carbon at the root of the branched chain, and P ¹ , P ² , and P ³ represent propylene-based heavy ions. Combined residues are indicated.
P ¹ , P ² , and P ³ may contain a branched carbon (Cbr) different from Cbr described in the structural formula (2) in itself.

Such a branched structure is identified by ¹³ C-NMR analysis. The assignment of each peak is described in Macromolecules, Vol. 35, no. 10. The description of 2002, pages 3839-3842 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) were observed, each at 43.9-44.1 ppm, 44.5-44.7 ppm, and 44.7-44.9 ppm. Methine carbon (Cbr) is observed at ˜31.7 ppm. Hereinafter, the methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as branched carbon (Cbr).
It is characterized in that three methylene carbons adjacent to the branched methine carbon Cbr are observed in three non-equivalent diastereotopics.

The branched chain assigned by ¹³ C-NMR referred to in the present invention represents a propylene polymer residue having 5 or more carbon atoms branched from the main chain of the propylene polymer. It can be distinguished from a branch having 4 or less carbon atoms by the difference in the peak position of the branched carbon (see Macromol. Chem. Phys. 2003, Vol. 204, p. 1738).

In general, considering the definition of the number of branches and the length of the polymer, the higher the number of branches, the better the melt properties. On the other hand, it is considered that if the number of branches is unevenly distributed between the molecules, a gel is generated and the effect of improving the melt properties is reduced.
The number of branches is defined as the number of branches (density) per 1000 total skeleton-forming carbons of the branched carbon (Cbr) observed at 31.5 to 31.7 ppm using the assignment by ¹³ C-NMR. . However, the total skeleton-forming carbon means all carbon atoms other than methyl carbon.

As a result of ¹³ C-NMR measurement, it can be seen that a small amount of branched components are present in the propylene polymer showing improved melt properties of the present invention. The amount is less than the quantification limit of 0.1, but there are 0.01 or more of the detection limit.
On the other hand, when the amount of branching is too large, there is a concern that gel is generated and the appearance of the molded product is impaired. Furthermore, there is a problem of causing deterioration of melt ductility.
Therefore, the number of branches is 0.01 or more as a lower limit and 0.4 or less as an upper limit.
Even when the current ¹³ C-NMR of high magnetic field NMR is used, the limit of quantification is 0.1 or more, and the quantification has not been achieved so far. When the branching was below the limit of quantification by ¹³ C-NMR, instead of this, branching was evaluated by a more sensitive rheological method. As a result, the obtained strain hardening degree (λmax) is defined to be 6.0 or more.

Moreover, in order to show high strain hardening like the propylene-type polymer of this invention, it is thought that 7000 or more which is an entanglement molecular weight of a polypropylene is required regarding branch length (reference: Macromolecules. 1998, 31, 1335, Macromolecules). 2002, 35, 10062).
This corresponds to about 400 or more in terms of the number of skeleton carbon atoms. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. It is considered that the melt physical properties are further improved as the branch length becomes longer.
Therefore, the branched chain length of the propylene-based polymer of the present invention is 500 or more skeleton carbon atoms (polypropylene molecular weight conversion: 11,000), preferably 1000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 21,000). More preferably, it has 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).

The polypropylene molecular weight converted value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Accordingly, the branch length of the propylene-based polymer of the present invention is 11,000 or more, preferably 21,000 or more, more preferably 42,000 or more in terms of number average molecular weight (Mn) measured by GPC, Replaced.

Further, when considering the polymerization mechanism, the macromer generated from the active species derived from the catalyst component [A-1] is incorporated into the main chain to form a branched structure, so that the average molecular weight of the macromer is that of the incorporated branched chain. Characterized as average molecular weight.
For example, in the propylene-based polymer of the present invention, when the molecular weight of the macromer generated from the active species derived from [A-1] is 50,000 in number average molecular weight, the average molecular weight of the incorporated branched chain is 50,000 Converted to skeleton carbon, it is interpreted as 2400.
The number average molecular weight of the macromer generated from the active species derived from the above [A-1] is based on the molecular weight when the polymerization is carried out by the peak top of the portion derived from [A-1] in GPC or [A-1] alone. Can be estimated.

On the other hand, the branched distribution of the polymer can be measured by GPC-vis or GPC-malls, but considering the polymerization mechanism, the macromer derived from [A-1] has a higher molecular weight and higher copolymerization. Considered that long chain branching is introduced into the molecular weight component derived from [A-2] because it is considered that branching is generated by incorporation into the active species derived from component [A-2]. ing.
Since the molecular weight component derived from the catalyst component [A-2] has a higher molecular weight than the molecular weight component derived from [A-1], the branched distribution has a high molecular weight side ([A-2] derived side). In addition, it is considered that the distribution form is introduced with branching.
In addition, the molecular weight component derived from [A-1] also has a branched structure formed by incorporating the macromer by [A-1] itself.
An example of the molecular weight distribution derived from [A-1] and [A-2] is shown in FIG.

Describing the relationship between the number of branches and the distribution of branches, in order to improve the melt physical properties, it is generally considered that a large number of branches is necessary, and in Patent Document 9 (Japanese Patent Laid-Open No. 2007-154121), A propylene homopolymer having a branch number of 0.1 / 1000 skeleton carbon or more is disclosed.
However, the strain hardening degree (λmax) in the measurement of the extensional viscosity of the disclosed propylene homopolymer is less than 6, and the strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer of the present invention is 6. Even if it is 0 or more, the improvement effect is not sufficient. This is because the desired branching component is not sufficiently introduced because it is produced from a single complex, meaning that the effect of improving the melt properties is small even if the number of branches is simply large on average.
The propylene-based polymer of the present invention does not necessarily have a large number of branches (average value) as compared with conventional branched polymers, but by introducing multiple branches into the high molecular weight side by combining a plurality of complexes. The melt properties are remarkably improved.

Further, the stereoregularity of the side chain will be described. The stereoregularity of the main chain and the side chain is determined by the stereoregular ability of [A-1] and [A-2] used, respectively. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is deteriorated. Therefore, in order to obtain a higher-rigidity polymer, it is preferable that the side chain and the main chain have high stereoregularity. As the value, both the main chain and the side chain are 95% or more in mm fraction. Especially preferably, it is 96% or more, More preferably, it is 97% or more.
The stereoregularity of the side chain is considered to be equal to the stereoregularity of the polymer by [A-1] alone.
The details of the stereoregularity of the main chain and side chain will be described later.

II. Properties of Propylene Polymer The propylene polymer of the present invention has an excellent balance between physical properties and melt processability with controlled melt fluidity (melt spreadability) and melt tension. The physical properties of the propylene polymer of the present invention will be described.
1. Melt flow rate (MFR)
As shown in the requirement (i), the propylene polymer of the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 Kg of 0.01 g / 10 min or more and 100 g / 10 min or less. Need to be.
MFR is an indicator of fluidity, and this value decreases as the molecular weight of the polymer increases, while this value increases as the molecular weight decreases. When this value is small, fluidity is deteriorated and melt spreadability is deteriorated. Accordingly, the MFR needs to be 0.01 g / 10 min or more, preferably 0.1 g / 10 min or more, and more preferably 0.3 g / 10 min or more.
On the other hand, when this value is large, the fluidity is improved, but the molecular weight is too small, which causes a deterioration in mechanical properties such that the impact strength is reduced when formed into a molded body. Therefore, the MFR needs to be 100 g / 10 min or less, preferably 20 g / 10 min or less, more preferably 10 g / 10 min or less.

The melt flow rate (MFR) is a test condition in accordance with JIS K6921-2 “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties”. : A value measured at 230 ° C. and a load of 2.16 kgf.
The melt flow rate (MFR) of the propylene polymer can be easily adjusted by changing the temperature and pressure conditions of propylene polymerization, or by adding a chain transfer agent such as hydrogen during polymerization as the most general technique. Can be done.

2. Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC
As shown in the requirement (ii) above, the propylene-based polymer of the present invention is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), Mw / Mn (Q Value) in the range of 3.5 or more and 10.5 or less.
The Q value is an index representing the spread of the molecular weight distribution, and the larger the value, the wider the molecular weight distribution. If the Q value is too small, the distribution is narrow, and the balance between melt spreadability and workability becomes poor. Accordingly, the Q value needs to be 3.5 or more, and is preferably a value larger than 4.0. More preferably, the value is greater than 4.5. On the other hand, if the Q value is too large, the amount of unnecessary (low) molecular weight components increases, which may deteriorate the melt ductility. Therefore, the Q value needs to be 10.5 or less, preferably less than 8.0, and more preferably less than 7.5.
The average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC of the propylene polymer can be changed by changing the temperature and pressure conditions of propylene polymerization, or the most common method is chain transfer such as hydrogen Adjustment can be easily made by a method of adding an agent during propylene polymerization. Furthermore, when using 2 or more types of the metallocene complex to be used, it can control by changing the quantity ratio.

3. Bias of molecular weight distribution obtained from molecular weight distribution curve by GPC toward high molecular weight side As shown in the above requirement (viii), the propylene polymer of the present invention has a peak position in the molecular weight distribution curve obtained by GPC. The common logarithm of the corresponding molecular weight is Tp, and the common logarithm of the molecular weight at the position where the peak height is 50% is L ₅₀ and H ₅₀ (L ₅₀ is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp) , Α and β are respectively defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , it is desirable that α / β is greater than 0.9 and less than 2.0. Here, α / β is an index representing the deviation of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created in which the common logarithm of molecular weight (MW) is plotted on the horizontal axis and the relative differential mass of the molecule corresponding to the MW is plotted on the vertical axis.
The molecular weight (MW) referred to here is the molecular weight of individual molecules constituting the propylene polymer, and is different from the weight average molecular weight (Mw) of the propylene polymer. FIG. 1 is a diagram showing an example of a molecular weight distribution curve. Α and β are obtained from the created graph. In the present invention, as described above, it is desirable that α / β is greater than 0.9 and less than 2.0.

Usually, when uniform polymerization is carried out with a catalyst having a single active site, the molecular weight distribution has the most probable distribution shape. The most probable distribution α / β is calculated as 0.9.
Therefore, the molecular weight distribution of the propylene-based polymer of the present invention means that the molecular weight distribution of the polymer polymerized uniformly at a single active site is further widened to the higher molecular weight side.
If α / β is 0.9 or less, the amount of the high molecular weight component is relatively insufficient, so that the melt tension and swell ratio become small, and the moldability deteriorates.
Therefore, it is desirable that the propylene-based polymer of the present invention has α / β larger than 0.9, preferably 1.0 or more, and more preferably 1.1 or more.

On the other hand, when α / β is 2.0 or more, the amount of the high molecular weight component is too large, which causes deterioration of melt ductility.
Therefore, the propylene-based polymer of the present invention desirably has α / β of less than 2.0, preferably less than 1.8, more preferably less than 1.7, and still more preferably less than 1.6. It is.
In the molecular weight distribution curve, two or more peaks may appear. In that case, the maximum peak can be replaced with the peak of the present invention. Also, if the H ₅₀ appears two or more may be replaced with the molecular weight of the lowest molecular weight side. Similarly, when two or more L ₅₀ appear, the molecular weight on the lowest molecular weight side can be replaced.
The bias toward the high molecular weight side of the molecular weight distribution obtained from the molecular weight distribution curve by GPC of the propylene-based polymer is selected after selecting one capable of producing a high molecular weight polymer as one of the two types of metallocene complexes used. Adjustment can be easily made by controlling the amount of hydrogen added during the polymerization. It can also be adjusted by changing the amount ratio of the two metallocene complexes used.

4). Ratio of components having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC As shown in the requirement (iii), the propylene-based polymer of the present invention has a total molecular weight in the molecular weight distribution curve obtained by GPC. On the other hand, the ratio of components having a molecular weight (M) of 2 million or more (W (2 million or more)) is 0.4% by weight or more and less than 10% by weight.
The ratio of 2 million or more (W (2 million or more)) is an index indicating the ratio of a very high molecular weight component contained in the polymer.
The very high molecular weight component ratio W (2 million or more) is an integral molecular weight distribution curve obtained by GPC (the total amount is normalized to 1), and the molecular weight (M) is 2 million (Log (M) = 6). .3) The integral value up to the following is defined as a value obtained by subtracting from 1. An example of the integrated molecular weight distribution curve is also shown in FIG.

As described above, when the amount of the high molecular weight component is insufficient, the melt tension and the swell ratio are decreased, and the moldability is deteriorated. Therefore, a component having a high molecular weight is necessary, and the moldability is efficiently improved by containing a small amount of a component having a very high molecular weight. This very high molecular weight component is considered to contain a branched component as described above.
Therefore, the propylene-based polymer of the present invention desirably has W (2 million or more) of 0.4% by weight or more, preferably 1.0% by weight or more, and more preferably 2.0%. % By weight or more.
However, when the ratio of this component is too high, the fluidity is deteriorated. In addition, since it is a component having a very high molecular weight, a gel is generated, resulting in a problem that the appearance of the molded product is impaired. Moreover, when the ratio of this component is too high, it will cause deterioration of melt ductility.
Therefore, the propylene-based polymer of the present invention desirably has W (2 million or more) less than 10% by weight, preferably less than 6.0% by weight, and more preferably less than 5% by weight.
In addition, the ratio of the component having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC of the propylene polymer is selected on the low molecular weight side after selecting a metallocene complex that can produce a high molecular weight polymer. The amount can be easily adjusted by controlling the amount ratio of the metallocene complex to the metallocene complex, the amount of hydrogen added during the polymerization of propylene, and the polymerization temperature.

  So far, adjustment methods related to the molecular weight of the propylene-based polymer such as the ratio of components having MFR, Q value, α / β and molecular weight (M) of 2 million or more have been described. For example, control of the amount of hydrogen can be given as a common control method. When the amount of hydrogen is increased, the MFR of the propylene polymer increases, and the ratio of components having a Q value, α / β, and molecular weight (M) of 2 million or more tends to decrease. On the other hand, it is possible to increase MFR by increasing the polymerization temperature or decreasing the monomer partial pressure. In this case, the ratio of components having a molecular weight (M) of 2 million or more decreases, but the Q value and α / β is not significantly affected. In addition, the ratio of components having a molecular weight (M) of 2 million or more with respect to MFR can be controlled by changing the amount and type of the metallocene complex that produces the high molecular weight side. In this way, the regulation can be controlled by changing the catalyst used and the polymerization conditions.

  The weight average molecular weight (Mw), Q value, α / β, and W (over 2 million) values defined above are all obtained by gel permeation chromatography (GPC). Details of the measuring method and measuring equipment 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

5. Elevated temperature elution fractionation with orthodichlorobenzene (ODCB) (TREF)
As shown in the above requirement (iv), for example, the propylene homopolymer is eluted at a temperature of 40 ° C. or lower in an elution curve obtained by temperature rising elution fractionation (TREF) measurement. The component is 3.0% by weight or less.
A component that elutes at a temperature of 40 ° C. or lower is a low crystalline component. If the amount of this component is large, the crystallinity of the entire product is lowered, and the mechanical strength such as the rigidity of the product is lowered.
Therefore, this amount needs to be 3.0% by weight or less, preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. .
Elevated temperature elution fractionation (TREF) of propylene-based polymer with orthodichlorobenzene (ODCB) can generally be kept low by using a metallocene complex, but the purity of the catalyst is kept above a certain level. In addition, it is necessary that the catalyst production method and the reaction conditions during the polymerization are not extremely high, and that the amount ratio of the organic aluminum to the metallocene complex is not excessively increased.

The details of the measurement method of the eluted component by temperature rising elution fractionation (TREF) are as follows.
A sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, and then cooled to 40 ° C. at a rate of 4 ° C./min, and held for 10 minutes. Thereafter, orthodichlorobenzene as a solvent is caused to flow through the column at a flow rate of 1 mL / min, and components dissolved in 40 ° C orthodichlorobenzene are eluted in the TREF column for 10 minutes, and then the heating rate is 100 ° C / hour. The column is linearly heated to 140 ° C. to obtain an elution curve.

Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inert treatment glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength infrared detector, manufactured by FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

6). Isotactic triad fraction (mm) measured by ¹³ C-NMR
As shown in the requirement (v), the propylene-based polymer of the present invention has a stereoregularity in which the mm fraction of the three propylene unit chains obtained by ¹³ C-NMR is 95% or more.
The mm fraction is the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control.
If the mm fraction is smaller than this value, the mechanical properties such as the elastic modulus of the product are lowered. Therefore, the mm fraction is preferably 96% or more, and more preferably 97% or more.
Further, the stereoregularity of the main chain and the side chain is determined by the stereoregulation ability of the catalyst components [A-1] and [A-2] used in the method for producing a propylene polymer described later. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is degraded. Therefore, in order to obtain a higher rigidity polymer, it is preferable that the side chain and the main chain have high stereoregularity. As the value, the main chain and the side chain are 95% or more in mm fraction. Especially preferably, it is 96% or more, More preferably, it is 97% or more.
The isotactic triad fraction (mm) measured by ¹³ C-NMR of the propylene polymer can be easily adjusted by the selection of the metallocene complex to be used and the polymerization temperature.

The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg was completely dissolved in 2.5 ml of deuterated 1,1,2,2, -tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.2 ppm in the middle of the three peaks of deuterated 1,1,2,2-tetrachloroethane. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768

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

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

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

  Moreover, the propylene polymer of the present invention may have the following partial structure containing an ethylene unit.

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

  Moreover, as a partial structure containing a position irregular unit, it may have the following structure (5-a), structure (5-b), structure (5-c), and structure (5-d).

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

The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm) and carbon F (38 in the position irregular substructure [structure (5-a)]). It can be evaluated from 1/4 of the sum of the peak areas of resonance at around .7 ppm.
The peak areas based on carbon A ′ are carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J It can be evaluated by 2/5 of the sum of peak areas (resonance around 34.1 ppm) and the sum of peak areas of carbon K (resonance around 33.7 ppm).
The peak area based on carbon A ″ can be evaluated by the sum of peak areas of carbon L (resonance in the vicinity of 27.7 ppm) of the position irregular partial structure [structure (5-d)].
The peak area based on carbon B can be evaluated by carbon J. The peak area based on carbon B ′ can be evaluated by carbon K.
Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
As described above, since the peak areas of mm, mr, and rr can be evaluated, it is possible to obtain the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center according to the above formula (I).

7). Strain hardening degree (λmax) in measurement of elongational viscosity
As shown in the requirement (vi), the propylene-based polymer of the present invention needs to have a strain hardening degree (λmax) of 6.0 or more in the measurement of elongational 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. As a result, uneven thickness is unlikely to occur during blow molding.
Therefore, the strain hardening degree is required to be 6.0 or more, preferably 10.0 or more, more preferably 12.0 or more, and further preferably 15.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain.
Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
At the present time, it is considered to be the most sensitive method for evaluating branching. Since the branched structure cannot be directly evaluated by ¹³ C-NMR, the strain hardening degree is used as an index of branching instead of the method. It was.

In general, in order to show a high degree of strain hardening, a branching length of 7,000 or more, which is an entanglement molecular weight of polypropylene, is required. When converted into skeleton carbon number, it corresponds to about 400 or more. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. It is considered that the melt physical properties are further improved as the branch length becomes longer. In particular, when a longer branched chain is introduced, strain hardening is considered to be detected even in a slower strain rate region in the measurement of elongational viscosity.
Therefore, as described above, the branched chain length of the propylene-based polymer of the present invention is 500 or more skeleton carbon atoms (polypropylene molecular weight conversion: 11,000), preferably 1000 skeleton carbon atoms (polypropylene molecular weight conversion: 2. 10,000) or more, and more preferably 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).
As described above, the polypropylene molecular weight conversion value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Accordingly, the branch length of the propylene-based polymer of the present invention is 11,000 or more, preferably 21,000 or more, more preferably 42,000 or more in terms of number average molecular weight (Mn) measured by GPC, Can be replaced. The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer is 6 or more by controlling the selection of two kinds of metallocene complexes constituting the catalyst used for propylene polymerization, the ratio of the amounts thereof, and the prepolymerization conditions. It can be enlarged. 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, long chain branches are uniformly distributed among the polymer particles.

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

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

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

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η _E (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before the strain hardening is approximated by a straight line, the maximum value (ηmax) of the elongational viscosity η _E until the strain amount becomes 4.0 is obtained, and the approximate straight line up to that time Let the upper viscosity be ηlin.
FIG. 4 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The strain rate can be measured in the range of 0.001 / sec to 10.0 / sec, and the strain hardening degree varies depending on the difference in strain rate. The strain rate dependence of the strain hardening degree is considered to change depending on the form and length of the introduced branch.

8). Memory effect (ME)
As for the propylene-type polymer of this invention, as shown to said requirement (vii), it is desirable that a memory effect (ME) satisfy | fills the following relational expression (I-1).
(ME) ≧ −0.26 × log (MFR) +1.9 (I-1)
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

In the propylene-based polymer of the present invention, preferably, a correlation between a memory effect (ME) that is an index that represents an abundance ratio of a high molecular weight component in a polymer and an MFR that is an index that represents an average molecular weight of the polymer is a specific relationship ( It is characterized by being in the above formula (I-1)).
ME is an index representing the non-Newtonian property of a polymer, and a large ME indicates that a component having a long relaxation time exists in the polymer. That is, when ME is large with the same MFR, it means that the long-term relaxation component is distributed in the polymer.
Further, it is empirically known that ME has a first-order correlation with Log (MFR), and generally, the larger the molecular weight (that is, the smaller the MFR value), the larger the ME value. .

The propylene-based polymer of the present invention is characterized in that the ME in the MFR match is larger than that of conventionally known polymers as shown in FIG. 5 due to the presence of a branching component in the polymer chain. When the amount of the long-term relaxation component is large, the melt tension is excellent. More preferably, the following relational expression (I-2) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.20 (I-2)
More preferably, the following relational expression (I-3) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.40 (I-3)

  The memory effect (ME) was measured using a melt indexer manufactured by Takara, and extruded at 190 ° C. with an orifice diameter of 1.0 mm and length of 8.0 mm under a load. The extrusion speed was 0.1 g. At the time of / min, the polymer extruded from the orifice is quenched in ethanol, and the value of the strand diameter at that time is divided by the orifice diameter.

9. Melt tension and melt spreadability The propylene-based polymer of the present invention has a controlled branch structure (branch amount, branch length, branch distribution), so that melt properties are remarkably improved. That is, it has excellent melt spreadability while having high melt tension. As an index of melt tension and melt spreadability, it can be expressed by a balance between melt tension (MT) and maximum winding speed (MaxDraw) measured by the following measuring method.

A method for measuring the melt tension (MT) and the maximum winding speed (MaxDraw) will be described.
Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the tension detected by the pulley when the resin is extruded in a string shape under the following conditions and wound on a roller is defined as a melt tension (MT).
Capillary: 2.1mm in diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 230 ° C.

When the winding speed is gradually increased from 4.0 m / min (acceleration: 5.4 cm / s ² ), the winding speed immediately before the string-like material is cut is the maximum winding speed (MaxDraw). To do.
Here, a larger MT value means higher melt tension, and a larger MaxDraw means better fluidity and spreadability.
The propylene-based polymer of the present invention has improved melt tension by broadening the molecular weight distribution and introducing branching. Therefore, MT is 5 g or more, preferably 10 g or more, more preferably 15 g or more. .

In addition, as described above, when the high molecular weight component is increased or the number of branches is increased, the MT value can be increased, but conversely, the polymer has too many high molecular weight components or the branches are unevenly distributed. Then, the viscosity becomes too high during winding, causing breakage of the string-like material, and MaxDraw does not increase. That is, the melt ductility is deteriorated.
The propylene-based polymer of the present invention can have a large MaxDraw while maintaining a high MT by controlling the branch component, and the balance between melt tension and melt spreadability is improved.
Therefore, the propylene polymer of the present invention has a MaxDraw of 10 m / min or more, preferably 20 m / min or more, and more preferably 30 m / min or more.

As explained above, the propylene-based polymer of the present invention is a long-chain branched type in which melt spreadability and melt tension are controlled and excellent in balance between physical properties and processability. In contrast to conventional propylene polymers, for example, as described above, Patent Document 9 (Japanese Patent Laid-Open No. 2007-154121) discloses a propylene homopolymer having a branch number of 0.1 / 1000 skeleton carbon or more. However, the degree of strain hardening (λmax) in the measurement of the extensional viscosity is less than 6, and the degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene-based polymer of the present invention is 6.0 or more, The effect of improving melt properties is not sufficient. In addition, in the commercial product of polypropylene that is crosslinked by electron beam irradiation and has a high degree of long-chain branching (base melt high melt tension polypropylene, “PF814”), the branched carbon of the structural formula (2) described above is not detected. In addition, the isotactic triad fraction (mm) by ¹³ C-NMR is low (92.5%), and further, molecular cleavage occurs simultaneously with crosslinking during irradiation with an electron beam, resulting in an increase in low molecular weight components. . In addition, as another general method for controlling the molding process characteristics, control is performed by expanding the molecular weight distribution. However, when the molecular weight distribution is expanded, the low molecular weight component is increased as a result. It is thought that stability (return property) is reduced.
However, the propylene-based polymer of the present invention is controlled by expanding the molecular weight distribution by broadening the molecular weight distribution and introducing branches, but the low molecular weight component does not increase and the high molecular weight component increases. Therefore, the above disadvantages do not occur.
Thus, since the propylene-based polymer of the present invention is a long-chain branched type, it has an excellent balance between physical properties and workability with controlled melt ductility and melt tension not found in conventional propylene-based polymers. It has become.

III. Propylene Polymer Production Method About the method of producing the propylene polymer of the present invention, the above-described melt ductility and melt tension, which are the characteristics of the present invention, are controlled and the long-chain branch has an excellent balance between physical properties and processability. There is no particular limitation as long as it is a method for obtaining a propylene-based polymer of the type, and examples of the method for introducing a controlled branched component include the following methods using a plurality of complexes.
That is, a method for producing the above-mentioned long-chain branched propylene polymer,
As a propylene polymerization catalyst, the following catalyst components (A), (B) and (C) are used, and a method for producing a propylene-based polymer is mentioned.
Catalyst component (A): From component [A-1] which is a compound represented by the following general formula (a1) and from component [A-2] which is a compound represented by the general formula (a2) At least one, two or more selected Group 4 transition metal compounds of the periodic table Component [A-1]: Compound represented by general formula (a1) Component [A-2]: Represented by general formula (a2) Compound Catalyst Component (B): Ion Exchange Layered Silicate Catalyst Component (C): Organoaluminum Compound

Hereinafter, the catalyst components (A), (B), and (C) will be described in detail.
(1) Catalyst component (A)
(I) Component [A-1]: Compound represented by general formula (a1)

[In General Formula (a1), each of R ¹¹ and R ¹² independently represents a heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms. In addition, each of R ¹³ and R ¹⁴ is independently halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a C 6-16 aryl that may contain a plurality of hetero elements selected from these Represents a heterocyclic group containing a group, nitrogen or oxygen having 6 to 16 carbon atoms, and sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

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

Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or, as the aryl group which may contain a plurality of hetero elements selected from these, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms You may have a containing hydrocarbon group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-tbutylphenyl group, a 2,3-dimethylphenyl group, a 3,5-ditbutylphenyl group, a 4-phenyl-phenyl group, or a chlorophenyl. Group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group, a 4-tbutylphenyl group, and a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In the general formula (a1), X ¹¹ and Y ¹¹ are auxiliary ligands and react with the cocatalyst of the component (B) to generate an active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, X ¹ and Y ¹ are not limited to the type of ligand, and each independently represents hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In the general formula (a1), Q ¹¹ is a silylene that may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4- Enyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-methyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-isopropyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-Methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4 -(4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, and the like. .

  Of these, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel are more preferable. Mylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethyl Silylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t -Butylphenyl) -indenyl}] hafnium.

(Ii) Component [A-2]: Compound represented by general formula (a2)

[In General Formula (a2), each of R ²¹ and R ²² is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent 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 ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. 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 contain a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5 -Dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like.

Further, the X ²¹ and Y ²¹ are auxiliary ligands to generate an active metallocene having olefin polymerizability reacts with the cocatalyst component (B). Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently hydrogen, halogen group, hydrocarbon group having 1 to 20 carbon atoms, carbon 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.

Q ²¹ is a binding group that crosslinks two conjugated five-membered ring ligands, and a silylene having a divalent hydrocarbon group having 1 to 20 carbon atoms and 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. 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.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a2) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound whose center metal is hafnium was described, it is obvious that the same zirconium compound can be used, and various ligands, crosslinking groups, or auxiliary ligands can be arbitrarily used.
Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-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- (4-chloro-2-naphthyl) -4-hydroazule Nil}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] 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-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl-] 4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1 1'-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-Methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 '-(9-silafluorene- 9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (2-fluoro- 4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) ) -4-hydroazurenyl}] hafnium, and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (B)
Next, the catalyst component (B) used in the present invention is an ion-exchange layered silicate.
(I) Types of ion-exchangeable layered silicate In the present invention, the ion-exchangeable layered silicate used as a raw material (hereinafter simply abbreviated as “silicate”) means that the surfaces formed by ionic bonds or the like have a binding force to each other. The silicate compound has a crystal structure stacked in parallel with each other, and the contained ions are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can. Depending on the type, amount, particle diameter, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in 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. You may include them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectite groups, vermiculite groups such as vermiculite, mica, illite, sericite, sea chlorite and other mica groups, attapulgite, sepiolite, palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

  The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of the catalyst component (B) according to the present invention can be used as it is without any particular treatment, but it is preferable to perform a chemical treatment. . Here, the chemical treatment of the ion-exchange layered silicate can be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute part or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In the present invention, a combination of the following acids and salts may be used as the treating agent. A combination of these acids and salts may also be used.

<Salt treatment>:
In the present invention, 40% or more, preferably 60% or more of the exchangeable Group 1 metal cation contained in the ion-exchangeable layered silicate before being treated with salts is dissociated from the salts shown below. It is preferable to ion exchange with cations.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Specific examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4 , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg ( PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.
Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

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

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.

Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

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

<Organic treatment>:
Examples of the organic treatment agent used for organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. It is not limited to these.

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

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (B).
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the catalyst component (B) after the removal is 3% by weight or less when the water content when dehydrating for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight, It is preferably 1% by weight or less.

  As described above, in the present invention, the catalyst component (B) is particularly preferably an ion-exchange layered silicic acid having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment. It is salt.

  The ion-exchange layered silicate is preferable because it can be treated with a catalyst component (C) described later before use as a catalyst or as a catalyst. Although there is no restriction | limiting in the usage-amount of the catalyst component (C) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

  The catalyst component (B) is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.

Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) used in the present invention is an organoaluminum compound. Organic aluminum compounds used as the catalyst component (C) has the general ^{_{formula: (AlR 11 q Z 3-}} q) a compound represented by _p is suitable.
In the present invention, it goes without saying that the compounds represented by this formula can be used singly, mixed in plural or in combination. In this formula, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively. R ¹¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, and a C 1 atom when it is an amino group. Eight amino groups are preferred.

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 having p = 1 and q = 3 are preferable. More preferably, R ¹¹ is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Catalyst Formation / Preliminary Polymerization The catalyst according to the present invention is formed by bringing the above-mentioned components into contact with each other in the (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. Can do.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When the catalyst component (C) is used, before the catalyst component (A) and the catalyst component (B) are contacted, the catalyst component (A), or the catalyst component (B), or the catalyst component (A) and the catalyst Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of the catalyst components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) used relative to the catalyst component (B) is preferably in the range of 0.01 to 1000 mmol, particularly preferably 0.05 to 500 mmol, with respect to 1 g of the catalyst component (B). Therefore, the amount of the catalyst component (C) relative to the catalyst component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 100 in terms of the molar ratio of the transition metal.

Although the ratio of component [A-1] and component [A-2] used by this invention is arbitrary in the range with which the characteristic of a propylene polymer is satisfy | filled, each component [A-1] and [A-2] The molar ratio of the transition metal of [A-1] to the total amount of is preferably 0.30 or more and 0.99 or less.
From component [A-1], a low molecular weight terminal vinyl macromer is produced, and from component [A-2], a high molecular weight product obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled. In order to produce a propylene-based polymer for applications requiring higher melt properties and high catalytic activity, it is particularly preferably 0.40 or more, and further preferably 0.5 or more. The upper limit is particularly preferably 0.90 or less, and more preferably 0.8 or less.
Further, it is possible to adjust the balance between the average molecular weight and the catalyst activity with respect to the amount of hydrogen used.

  The catalyst according to the present invention is subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt properties can be improved thereby.

  The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (B). Moreover, a component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.

  In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of Catalyst / Propylene Polymerization As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst including the catalyst components (A), (B) and (C) and the monomer efficiently contact each other. .
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

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 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.2 MPa or more is preferable, and 1.5 MPa or more is more preferable. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Further, hydrogen can be used as a molecular weight regulator and for the purpose of improving the activity.
Hydrogen is used in a feed ratio of 0 to 1 mol% with respect to propylene, preferably 0.0001 mol% or more, and more preferably 0.001 mol% or more.
By changing the amount of hydrogen used, in addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, distribution) The melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.

The propylene-based polymer used in the present invention may be a propylene homopolymer, or, in addition to a propylene monomer, an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer. It may be a propylene α-olefin copolymer obtained by copolymerization. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and a plurality of the above-mentioned comonomers can be used. Specifically, they are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.
Among these, in order to obtain the propylene polymer of the present invention in a good balance between melt properties and catalytic activity, it is preferable that the comonomer such as ethylene be 5 mol% or less. In order to obtain a polymer having particularly high rigidity, the comonomer contained in the polymer should be 1 mol% or less, and propylene homopolymerization is more preferable.

(6) Consideration of polymerization mechanism It is considered that the formation of a macromer is generated by a special chain transfer reaction generally called β-methyl elimination. In the present invention, the component [A-1] having a specific structure is In a relatively low temperature range (40 ° C. to 80 ° C.), the selectivity of the β-methyl elimination reaction during the growth termination reaction is high, and the ratio of the β-methyl elimination reaction to the polymer growth reaction is that of the conventional structure. The inventors have found that it is larger than the complex.
Conventionally, in order to preferentially cause the β-methyl elimination reaction, it could only be produced under special conditions (low pressure, high temperature polymerization, no hydrogen addition) in slurry polymerization with a low propylene concentration, By using component [A-1] having a specific structure of the present invention, industrially effective bulk polymerization and gas phase polymerization, and practical pressure conditions (1.0 to 3.0 MPa) and temperature conditions It was found that the production was possible under (40 ° C. to 80 ° C.).

Furthermore, surprisingly, by adding hydrogen, in the conventional method, the chain transfer reaction by hydrogen is superior to the β-methyl elimination reaction, whereas the cause is unknown, but The propylene-based polymer production method is characterized by a small change in the balance between macromer formation and growth reaction even when hydrogen is added, and it has been found that the selectivity of the macromer remains almost unchanged even in the presence of hydrogen. Moreover, hydrogen has an activity improving effect.
This is because, in the past, it has been necessary to perform a multi-stage polymerization in which a macromer copolymerization is performed after a macromer generation step which is a special condition (low pressure, high temperature, no hydrogen addition), whereas the component [A-2 ], It was found that the macromer production step and the macromer copolymerization step can be performed under the same conditions, that is, simultaneous polymerization and single-stage polymerization can be performed.

On the other hand, since the component [A-2] has a specific structure, it has a high ability to copolymerize a macromer even though it does not have the ability to form a terminal vinyl structure, and further compared to the component [A-1]. And has the ability to produce higher molecular weight polymers. Further, when hydrogen is added, the activity is improved, and the molecular weight is lowered due to chain transfer by hydrogen.
Conventionally, macromer formation and macromer copolymerization are produced by a single complex, that is, in order to produce a polymer with the same complex of component [A-1] and component [A-2], If either the capacity or the macromer copolymerization capacity is insufficient, the amount of branching component introduced is insufficient on the high molecular weight side, or if hydrogen is used to adjust the molecular weight, the production amount of the macromer itself decreases. There was a problem of doing.

However, in the present invention, the component [A-1] having a specific structure having macromer generation ability and the component [A-2] having a specific structure having high molecular weight and macromer copolymerization ability are combined in a specific method. By using it as a catalyst, it is an industrially effective method such as bulk polymerization or gas phase polymerization, especially in single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It has been found that it is possible to produce a long-chain branched propylene-based polymer having the following physical properties:
Further, conventionally, it has been necessary to increase the branch generation efficiency by reducing the crystallinity by using a component having low stereoregularity, but in the method of the present invention, a component having sufficiently high stereoregularity, It can be introduced into the side chain by a simple method.

2. Ingredient (B)
In the propylene-based resin composition of the present invention, in addition to the component (A), a hydrogenated product (b1) of a specific styrene / conjugated diene block copolymer described below (hereinafter simply referred to as “component (b1)”) ), Ethylene / α-olefin copolymer rubber (b2) (hereinafter sometimes simply referred to as “component (b2)”), or ethylene polymer resin (b3) (hereinafter referred to as “component (b2)”). In addition, at least one thermoplastic resin (B) (hereinafter sometimes simply referred to as “component (B)”) selected from the “component (b3)” may be used as an essential component. . At least one component (B) is appropriately added depending on the use. The component (b1) to the component (b3) have slightly different functions and effects. The low temperature impact property and melt tension are added by the addition of the component (b1), the low temperature impact property is added by the addition of the component (b2), and the component ( The melt tension can be improved by the addition of b3).

(1) Component (b1): Hydrogenated product of styrene / conjugated diene block copolymer The hydrogenated product of styrene / conjugated diene block copolymer used in the present invention is a block using butadiene, isoprene or the like as the conjugated diene. This is a hydrogenated copolymer, such as styrene / ethylene / butylene / styrene (SEBS) or styrene / ethylene / propylene / styrene (SEPS), as well as hydrogenated block copolymer of styrene, butadiene and isoprene. There are things. Here, styrene derivatives such as α-methylstyrene and p-methylstyrene can also be used as styrene.
By blending a hydrogenated product of these styrene / conjugated diene block copolymers, the melt tension is improved and the drawdown resistance in hollow molding is improved, which is very effective for large-scale hollow molding. However, this blending reduces the melt fracture rate and makes it difficult to stretch, so in the case of hollow molding with a large blow ratio such as a deep-drawn shape or a complicated shape mold, the spreadability such as parison tearing or uneven thickness of the molded product is reduced. In addition to problems, it is not preferable to add a large amount because the economical efficiency of the composition is impaired.
The hydrogenated styrene / conjugated diene block copolymer used here is not particularly limited as long as a hollow molded body satisfying the above-mentioned requirements can be obtained, but the density in ISO 2781 is 0.90. What has 0.92 g / cm < ³ >, a styrene content of 31-35 weight%, and the viscosity by BMS0380 method is 1-2 Pa * s.

(2) Component (b2): Ethylene / α-olefin copolymer rubber In the present invention, ethylene / α-olefin copolymer rubber can be added for improving paintability and the like.
The ethylene / α-olefin copolymer rubber used in the present invention is a copolymer rubber using propylene, butene-1, hexene-1, octene-1, etc. as an α-olefin, and as a third component. It may be a terpolymer rubber (so-called EPDM) containing a non-conjugated diene such as ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene and the like. The Mooney viscosity [ML1 + 4 (121 ° C.)] (based on ASTM D1646) of these ethylene / α-olefin copolymer rubbers is 5 or more, preferably 10 or more, more preferably 20 to 40. If the Mooney viscosity is in the above range, it is preferable that the drawdown resistance of the composition is deteriorated and the shapeability at the time of molding is suppressed.
The density of the ethylene · alpha-olefin copolymer rubber used in the present invention is preferably 0.890 g / cm ³ or less, more preferably 0.885 g / cm ³ or less.

(3) Component (b3): Ethylene polymer resin As the ethylene polymer resin used in the present invention, in addition to the ethylene homopolymer, other main components such as ethylene, butene-1, and hexene-1 are used. Examples include copolymers with monomers, and specific examples include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. The ethylene polymer resin is effective in improving the drawdown resistance.
From the viewpoint of the surface quality and paintability of the molded product, an ethylene polymer resin having an MFR ([230 ° C., 21.18 N load] of 0.3 to 2 g / 10 min and a density of 0.920 g / cm ³ or more is particularly preferable. A high density polyethylene having an MFR [230 ° C., 21.18 N load] of 0.3 to 2 g / 10 min and a density of 0.940 g / cm ³ or more is preferable.

3. Compounding amount of component (A) The component component (A) is blended in an amount of 50 to 99% by weight of the propylene polymer of component (A), and 1 to 50% of component (B). (The total amount of the component (A) and the component (B) is 100% by weight), preferably the component (B) is 2 to 40% by weight, more preferably 3 to 35% by weight.
Here, when there are too few compounding quantities of a component (B), drawdown resistance and low temperature impact resistance will fall. When there is too much compounding quantity of a component (B), melt extensibility will deteriorate and it will become impossible to shape | mold.

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

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

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

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

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the physical-property measurement, analysis, etc. in a following example follow the following method.

1. Physical property measurement method, analysis method, evaluation method (1) Melt flow rate (MFR):
In accordance with JIS K6921-2, “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties” Test flow: 230 ° C., load 2 .16 kgf) was measured. The unit is g / 10 minutes.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Q value):
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(3) ME (memory effect):
Polymer that was extruded through an orifice at a temperature of 190 ° C and an orifice diameter of 1.0 mm and a length of 8.0 mm under load at a temperature of 0.1 g / min. Was quenched in ethanol and calculated as a value obtained by dividing the value of the strand diameter at that time by the orifice diameter. This value correlates with Log (MFR), and a large value indicates that the product appearance is improved when the swell is large and injection molded.
(4) mm fraction:
The measurement was carried out by the method described in the present specification using GSX-400 and FT-NMR manufactured by JEOL. The unit is%.
(5) Measurement of ethylene content:
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.

(6) Elongation viscosity:
It was measured by the method described in the present specification.
(7) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.
(8) Melting point (Tm) and crystallization temperature (Tc)
Using a Seiko Instruments DSC6200, the sheet-shaped sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. The crystallization temperature (Tc) is obtained as the maximum crystal peak temperature (° C.) when the temperature is lowered to 20 ° C., and then the maximum melting peak when the temperature is increased to 200 ° C. at 10 ° C./min. The melting point (Tm) was determined as the temperature (° C.).
(9) Drawdown resistance: Automotive bumper with resin temperature of 220 ° C, length of 2.2m, width of 0.4m, and weight of 8kg using Plako DA-100 large blow molding machine When the ratio of the upper wall thickness to the lower wall thickness of the molded body was 0.8 to 1.0, the one with less than 0.8, or the molding failure or the molding failure was judged as defective.
(10) Flexural modulus: measured in accordance with JIS K7203 at a bending speed of 2 mm / min at 23 ° C. The product physical property is preferably 1000 MPa or more.

(11) Izod impact strength: Measured with a notch at a temperature of −30 ° C. in accordance with JIS-K7110. The product physical property is preferably 4 kg / cm ² or more. Preferably, it is 5 kg / cm ² or more.
(12) Thermal stability (return property): Using a Plako DA-100 type large blow molding machine, the resin temperature is 220 ° C., the length is 2.2 m, the width is 0.4 m, and the weight is 8 kg. Molded automotive bumper. The bumper was pulverized with a pulverizer and again molded with a large blow molding machine. “◎” indicates that the product can be commercialized even if it is repeated 5 times or more. “○” indicates that the product can be commercialized even if it is repeated 3 or more times but less than 5 times. ”,“ XX ”means that the drawdown is large and the product cannot be repeatedly manufactured once.

2. 2. Production of raw materials 2-1. Production of propylene polymer (A) [Synthesis Example 1 of catalyst component (A)]:
(1) Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) indenyl}] hafnium: (component [A-1] (Synthesis of Complex 1):
(1-a) Synthesis of 4- (4-t-butylphenyl) -indene:
1-Bromo-4-t-butyl-benzene (40 g, 0.19 mol) and dimethoxyethane (400 ml) were added to a 1000 ml glass reaction vessel, and cooled to -70 ° C. A t-butyllithium-pentane solution (260 ml, 0.38 mol, 1.46 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The mixture was cooled again to −70 ° C., and a dimethoxyethane solution (100 ml) of triisopropyl borate (46 ml, 0.20 mol) was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.

Distilled water (100 ml) was added to the reaction solution, and the mixture was stirred for 30 minutes, and then sodium carbonate 50 g in water (150 ml), 4-bromoindene (30 g, 0.15 mol), tetrakis (triphenylphosphino) palladium (5 g, 4 g .3 mmol) was added in turn, after which the low boiling components were removed and heated at 80 ° C. for 5 hours.
The reaction solution was poured into ice water (1 L), from which ether was extracted three times, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 4- (4-tert-butylphenyl) -indene (37 g, yield 98%) as a pale yellow liquid.

(1-b) Synthesis of 2-bromo-4- (4-t-butylphenyl) -indene:
To a 1000 ml glass reaction vessel, 4- (4-t-butylphenyl) -indene (37 g, 0.15 mol), dimethyl sulfoxide (400 ml) and distilled water (11 ml) were added, and N-bromosuccinimide (35 g) was added thereto. , 0.20 mol) was gradually added, and the mixture was stirred at room temperature for 1 hour.
The reaction solution was poured into ice water (1 L), and extracted from it three times with toluene. The toluene layer was washed with saturated brine, p-toluenesulfonic acid (4.3 g, 22 mmol) was added, and the mixture was heated to reflux for 2 hours while removing moisture.
The reaction solution was transferred to a separatory funnel and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to give 2-bromo-4- (4-t-butylphenyl) -indene (46 g, yield 95%) as a pale yellow solid. Obtained.

Synthesis of (1-c) 4- (4-t-butylphenyl) -2- (5-methyl-2-furyl) -indene:
Methyl furan (13.8 g, 0.17 mol) and dimethoxyethane (400 ml) were added to a 1000 ml glass reaction vessel and cooled to -70 ° C. An n-butyllithium-hexane solution (111 ml, 0.17 mol, 1.52 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to 70 ° C., and a dimethoxyethane solution (100 ml) containing triisopropyl borate (41 ml, 0.18 mol) was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water (50 ml) was added to the reaction solution, and the mixture was stirred for 30 minutes, and then an aqueous solution (100 ml) of sodium carbonate 54 g, 2-bromo-4- (4-t-butylphenyl) -indene (46 g, 0.14 mol), Tetrakis (triphenylphosphino) palladium (5 g, 4.3 mmol) was added in order, and then heated while removing low boiling components and heated at 80 ° C. for 3 hours.
The reaction solution was poured into ice water (1 L), from which ether was extracted three times, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, the residue was purified with a silica gel column, recrystallized with hexane, and 4- (4-t-butylphenyl) -2- (5-methyl-2-furyl)- Indene (30.7 g, 66% yield) was obtained as colorless crystals.

Synthesis of (1-d) dimethylbis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} silane:
4- (4-t-Butylphenyl) -2- (5-methyl-2-furyl) -indene (22 g, 66 mmol) and THF (200 ml) are added to a 1000 ml glass reaction vessel and cooled to -70 ° C. did. An n-butyllithium-hexane solution (42 ml, 67 mmol, 1.60 mol / L) was added dropwise thereto. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to −70 ° C., 1-methylimidazole (0.3 ml, 3.8 mmol) was added, and a THF solution (100 ml) containing dimethyldichlorosilane (4.3 g, 33 mmol) was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethylbis (2- (5-methyl-2-furyl) -4- (4-t-butylphenyl))-indenyl) A pale yellow solid of silane (22 g, 92% yield) was obtained.

Synthesis of (1-e) rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium:
In a 500 ml glass reaction vessel, 9.6 g (13.0 mmol) of dimethylbis (2- (5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl) silane, 300 ml of diethyl ether. And cooled to -70 ° C in a dry ice-methanol bath. 16 ml (26 mmol) of a 1.59 mol / liter n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 250 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.2 g (13.0 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallization was performed with dichloromethane / hexane, and dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl)- Indenyl}] 1.3 g of hafnium racemate (purity 99% or more) was obtained as yellow-orange crystals (yield 22%).

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 0.95 (s, 6H), δ 1.18 (s, 18H), δ 2.09 (s, 6H), δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ6. 75 (dd, 2H), δ 7.09 (d, 2H), δ 7.34 (s, 2H), δ 7.33 (d, 2H), δ 7.35 (d, 4H), δ 7.87 (d, 4H ).

[Synthesis Example 2 of Catalyst Component (A)]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium: (component [A-1] (complex 2) Synthesis):

Synthesis of (1-a) dimethylbis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} silane:
Synthesis was performed according to the method described in Example 1 of JP-A-2004-124044.

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

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

[Synthesis Example 3 of Catalyst Component (A)]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: (synthesis of component [A-2] (complex 3) ):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. As well as.

[Synthesis Example 4 of Catalyst Component (A)]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium: (component [A-2] (complex 4) Synthesis):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium is described in Example 1 of JP 2000-95791 A. Was carried out in the same manner as described in.

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

(1-2) Catalyst preparation and prepolymerization:
In a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (65 mL) was added to form a slurry. .6 mL) and stirred for 1 hour, washed with heptane to a residual liquid ratio of 1/100, and heptane was added to a total volume of 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-t-butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (solution 1), and further, the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium (45 μmol) prepared in Example 4 was dissolved in toluene (12 mL). (Solution 2).

After adding triisobutylaluminum (0.6 mmol: 0.83 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, add the above solution 1, and then add the above solution 2 after 5 minutes. And stirred at room temperature for 1 hour.
Thereafter, 356 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, the propylene feed was stopped, the temperature was raised to 50 ° C., and residual polymerization was performed until the pressure in the autoclave reached 0.05 MPa. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.3 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 2 hours to obtain 29.5 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.95 (preliminary polymerization catalyst 1).

[Catalyst synthesis example 2]:
In (1-2) catalyst preparation and prepolymerization in catalyst synthesis example 1, rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl) prepared in synthesis example 2 of the catalyst component (A) was prepared. 2-furyl) -4-phenyl-indenyl}] hafnium (135 μmol) was dissolved in toluene (38 mL) to form solution 1, and rac-dichloro [1,2] prepared in Synthesis Example 3 of the catalyst component (A) was prepared. 1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium (15 μmol) was dissolved in toluene (4 mL) and used as solution 2 except for using catalyst synthesis example 3 A similar experiment was conducted.
As a result, 28.4 g of a dry prepolymerized catalyst was obtained. The prepolymerization ratio was 1.84 (preliminary polymerization catalyst 2).

[Polymerization Example 1]:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (143 mg / mL), 180 Nml of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 150 mg of the prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, 5 ml of ethanol was injected to stop the polymerization.
As a result, 356 g of a propylene polymer (LCB-1) was obtained. The outline of this polymerization example is shown in Table 1.
Table 2 shows the evaluation results of the obtained polymer samples.

[Polymerization Example 2]:
The 3 L autoclave was dried well by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (143 mg / mL) and then introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 600 mg of the prepolymerized catalyst 2 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 3 hours, 5 ml of ethanol was injected to stop the polymerization.
As a result, 477 g of a propylene polymer (LCB-2) was obtained. The outline of this polymerization example is shown in Table 1.
Table 2 shows the evaluation results of the obtained polymer samples.

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

[Example 2]
LCB-1 as the propylene polymer, and Engage 8150 manufactured by Dow Chemical as the ethylene / α-olefin copolymer rubber (density 0.868 g / cm ³ , MFR 1.0 g / 10 minutes, Mooney viscosity 33 ethylene / octene copolymer) Polymer rubber) is blended in the proportions shown in Table 3, mixed uniformly with a mixer, melt-kneaded with a twin screw extruder, extruded at an extrusion temperature of 200 ° C, cooled and granulated, pelletized. A composition was obtained. The obtained pellets were evaluated by various evaluation methods. The evaluation results are shown in Table 3.

[Example 3]
Evaluation was performed in the same manner as in Example 1 except that LCB-2 was used as the propylene polymer. The evaluation results are shown in Table 3.

[Example 4]
LCB-1 as a propylene polymer, Novatec HB332R (density 0.952 g / cm ³ , MFR 0.3 g / 10 min high density polyethylene) and ethylene / α-olefin copolymer as an ethylene polymer resin Using Dow Chemical's Engage 8150 as a rubber, blended in the proportions shown in Table 3, mixed uniformly with a mixer, melt-kneaded with a twin screw extruder, extruded at 200 ° C to cool down, cut and cooled. A granulated pellet-like composition was obtained. The obtained pellets were evaluated by various evaluation methods. The evaluation results are shown in Table 3.

[Example 5]
LCB-1 as a propylene polymer, Clayton G1651 as a hydrogenated styrene / conjugated diene block copolymer, Engage 8150 as an ethylene / α-olefin copolymer rubber, and talc (specific surface area 44) as an inorganic filler. , 1,000 cm ² / g, average particle size is 1.6 μm, component having a particle size of 10 μm or more 0.5% by weight, MgO component 33.1% by weight, SiO ₂ component 62.5% by weight, other 0.45% by weight) Are blended in the proportions shown in Table 3 and mixed uniformly with a mixer, then melt kneaded with a twin screw extruder, extruded at 200 ° C., extruded, cooled, granulated, and pelletized. Obtained. The obtained pellets were evaluated by various evaluation methods. The evaluation results are shown in Table 3.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that PF814 manufactured by Basel Co., Ltd., which is commercially available as high melt tension polypropylene, was used as the propylene polymer. The evaluation results are shown in Table 3. PF814 is a propylene homopolymer introduced with a long-chain branched structure subjected to electron beam treatment.

[Comparative Example 2]
Evaluation was performed in the same manner as in Example 2 except that PF814 was used as the propylene polymer. The evaluation results are shown in Table 3.

[Comparative Example 3]
Evaluation was performed in the same manner as in Example 4 except that PF814 was used as the propylene polymer. The evaluation results are shown in Table 3.

  As is clear from Tables 2 and 3, the propylene-based resin compositions having the compositions shown in Examples 1 to 5 that satisfy the respective requirements in the essential constituent elements of the present invention are all drawdown resistance and physical property balance. In addition, the surface smoothness and the thermal stability are remarkably improved, and it has suitable performance for automobile exterior parts such as bumpers. On the other hand, the propylene resin compositions having the compositions shown in Comparative Examples 1 to 3 are inferior in thermal stability (returnability).

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

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

It is a figure which shows an example of the molecular weight distribution curve in GPC. It is a figure of the description of the baseline of a chromatogram in GPC, and an area. It is a figure which shows an example of the molecular weight distribution derived from [A-1] in GPC, and [A-2] origin. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer.

Claims (4)

Propylene polymer (A) satisfying the following requirements (i) to (vi): 50 to 99% by weight, hydrogenated product of styrene / conjugated diene block copolymer (b1), Mooney viscosity [ML1 + 4 (121 ° C.) ] 5 or more ethylene / α-olefin copolymer rubber (b2), or MFR [230 ° C., 21.18 N load] is 0.3 to 2 g / 10 min, and the density is 0.920 g / cm ³ or more. A propylene-based resin composition comprising 1 to 50% by weight of at least one thermoplastic resin (B) selected from ethylene polymer resin (b3).
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.01 g / 10 min or more and 100 g / 10 min or less.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm fraction) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more. The propylene-based resin composition according to claim 1, wherein the propylene-based polymer (A) further satisfies the following requirement (vii).
Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ] The propylene-based resin composition according to claim 1 or 2, wherein the propylene-based polymer (A) further satisfies the following requirement (viii).
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.   The blow molded object which consists of a propylene-type resin composition as described in any one of Claims 1-3.

Images