JP5140625B2 - Propylene resin composition, food container using the same, and medical member - Google Patents

Description

  The present invention relates to a propylene-based resin composition, a food container using the same, and a medical member, and more specifically, by having a high swell ratio, the molding processability is remarkably improved and also has heat resistance. Therefore, it is related with the propylene-type resin composition which can be used suitably as a food container and a medical member, a food container using the same, and a medical member.

Conventionally, polypropylene has the characteristics of high melting point, high tensile strength, high rigidity, and chemical resistance, and thus has been widely used in many fields.
Recently, there has been a demand for a polypropylene resin composition capable of molding a thinner molded product in a shorter molding time. In addition, due to the rise in raw material prices due to naphtha soaring, there is a strong demand for materials that can be reduced in weight and that have the original characteristics of polypropylene, ie, high rigidity.

  One of the means for solving this problem is a technique using a so-called “high fluidity material” with an increased MFR. Although the high fluidity material has improved moldability and a thin molded product can be obtained, there is a problem that a flow mark is easily generated. A flow mark is a trasima-like pattern appearing on the surface appearance of a molded product, and a molded product in which the flow mark is generated impairs the design as a product, and the product value is remarkably lowered.

  For example, Patent Document 1, Patent Document 2, and Patent Document 3 disclose flow mark improvement techniques. However, even if these techniques are used, it has not been possible to obtain a food container or medical member in which a flow mark does not substantially occur depending on the thickness of the molded product.

JP 2001-288331 A JP 2002-12734 A JP 2004-18647 A

  An object of the present invention is to provide a propylene-based resin composition having heat resistance and high rigidity, suitable for food containers and medical members, and having good flow characteristics and improved moldability in view of the problems of the prior art. And it is providing the food container and medical member using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific propylene polymer (M) and a specific homopolypropylene, or an ethylene-propylene copolymer having an ethylene content of 0.5% by weight or less. By forming a propylene-based resin composition in which the polymer (H) is mixed at a specific ratio, it has characteristics such as heat resistance and high rigidity, which are suitable for food containers and medical parts, and has good flow characteristics. As a result, the present invention has been completed.

That is, according to the first invention of the present invention, 1 to 50% by weight of the propylene polymer (M) and 50 to 99% by weight of homopolypropylene, or ethylene having an ethylene content of 0.5% by weight or less. A propylene-based resin composition comprising a propylene copolymer (H),
The propylene polymer (M) satisfies the requirements defined in the following (i) to (vi), and homopolypropylene or an ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less is The propylene-based resin composition is provided that satisfies the requirements defined in the following (vii) to (ix).
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.1 g / 10 min or more and 100 g / 10 min or less,
(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,
(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 10 wt% or less,
(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,
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more,
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.
(Vii) the isotactic pentad fraction is 95% or more,
(Viii) Homopolypropylene or ethylene-propylene copolymer (H) has a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000,
(Ix) MFR (230 ° C., 2.16 kg load) is 10 to 100 g / 10 min.

According to the second invention of the present invention, in the first invention, there is further provided a propylene-based resin composition characterized by satisfying the requirements defined in the following (x).
(X) (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 a third invention of the present invention, in the first or second invention, the propylene polymer (M) further satisfies the requirements defined in the following (xi): A resin composition is provided.
(Xi) 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 that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, 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 and 2 0.0 or less.

On the other hand, according to a fourth aspect of the present invention, there is provided a food container according to any one of the first to third aspects, wherein the food container is formed by molding the propylene-based resin composition.
According to a fifth aspect of the present invention, there is provided a food container according to the fourth aspect, wherein the propylene-based resin composition is injection molded.
Furthermore, according to the sixth invention of the present invention, there is provided a food container characterized in that the thickness is 0.2 to 2.0 mm in the fourth or fifth invention.
On the other hand, according to a seventh aspect of the present invention, there is provided a medical member according to any one of the first to third aspects, wherein the propylene-based resin composition is molded.
According to an eighth aspect of the present invention, there is provided a medical member characterized in that the propylene-based resin composition is injection molded in the seventh aspect.
Furthermore, according to the ninth invention of the present invention, in the seventh or eighth invention, there is provided a medical member having a thickness of 0.2 to 2.0 mm.

The propylene-based resin composition of the present invention has characteristics of heat resistance and high rigidity, and has good flow characteristics and can improve moldability.
In particular, this propylene resin composition specifies a propylene polymer (component M) as a modifier to homopolypropylene or an ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less. Since the amount is added, while maintaining the fluidity of the component H, the improvement effect of the flow mark by the component M can be expected, and because of their excellent characteristics, various molded products obtained by injection molding, thermoforming, etc. In particular, it can be suitably used for food containers and medical members. Therefore, it is suitable for baked pudding containers or medical instruments that require heat treatment. Further, because of these excellent properties, it is excellent in moldability and can be suitably used for foam molding, sheet molding, blow molding and the like.

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 base line 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. It is a figure which shows an example of the extensional viscosity curve of a propylene-type polymer (a subscript represents strain rate: / sec).

The propylene resin composition of the present invention comprises 1 to 50% by weight of propylene polymer (M) and 50 to 99% by weight of homopolypropylene or ethylene-propylene copolymer having an ethylene content of 0.5% by weight or less. It is composed of coalescence (H).
Hereinafter, the components of the propylene-based resin composition, the production of the propylene-based resin composition, and uses will be sequentially described for each item.

I. Component of propylene-based resin composition The propylene-based polymer according to the present invention includes the following (i) to (vi), or in addition to these, (x) and / or (xi), or in addition to them Furthermore, it has the characteristics and properties of (xii) and / or (xiii).
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.1 g / 10 min or more and 100 g / 10 min or less.
(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.
(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 10% by weight or less.
(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.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.

(X) (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. ]
(Xi) 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 that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, 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 and 2 0.0 or less.

(Xii) (MT230 ° C.) ≧ 5 g
[In the formula, MT230 ° C. is measured using a melt tension tester, capillary: diameter 2.1 mm, cylinder diameter: 9.6 mm, cylinder extrusion speed: 10 mm / min, winding speed: 4.0 m / min, temperature: 230 It represents the melt tension when measured under the condition of ° C. ]
(Xiii) (MaxDraw) ≧ 10 m / min [where MaxDraw (maximum winding speed) is the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. Represent. ]

II. Propylene Polymer Structure, Long Chain Branch Structure Definition and Identification Method The propylene polymer according to 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.
In the propylene polymer according to the present invention, the melt properties are remarkably improved by introducing the long chain branching.
In general, ¹³ C-NMR is used to directly detect and quantify 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, the flow activation energy in linear viscoelasticity measurement and the strain hardening degree in elongational viscosity measurement are generally used at this stage as a method for detecting a minute amount of branching.
Regarding the branched structure, it is 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 presumed to be incorporated into the active species derived from the catalyst component [A-2] having a better copolymerizability, and the macromer copolymerization proceeds.
Therefore, the propylene polymer according to 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 13C-NMR measurement, the propylene polymer (M) exhibiting improved melt properties in the present invention has a trace amount of branched components, and the amount thereof is about 0.1.
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 that when the film is stretched at a high speed at the time of molding, so-called melt ductility is deteriorated, that is, the melt breaks. Therefore, the upper limit of the number of branches is 0.4 or less, preferably 0.2 or less. The lower limit is 0.01 or more.
Even when the current 13C-NMR of high magnetic field NMR is used, if measurement is not performed for a very long time, quantification is difficult with a small amount of about 0.1. When the amount of branching was small, 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 polymer (M) according to the present invention, it is considered that a branching length of 7000 or more, which is an entanglement molecular weight of polypropylene, is necessary (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 (M) according to 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).

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.
Therefore, the branch length of the propylene-based polymer according to 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 polymer (M) according to 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 There are 50,000, and it is interpreted as 2400 when converted into skeleton carbon.
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. It is considered that a long chain branch is introduced into the molecular weight component derived from [A-2] because it is considered that a branch is formed by incorporation into the active species derived from the component [A-2]. The
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 branch distribution, it is generally considered that a large number of branches is necessary in order to improve the melt properties. Japanese Patent Application Laid-Open No. 2007-154121 discloses that the number of branches is 0.1 / A propylene homopolymer having 1000 skeleton carbons 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 6.0, and the degree of strain hardening in the measurement of the extensional viscosity of the propylene-based polymer (M) according to the present invention. Even when (λmax) is 6.0 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 (M) according to the present invention does not necessarily have a large number of branches (average value) as compared with conventional branched polymers, but by combining a plurality of complexes, the branching is also performed on the high molecular weight side. By introducing it, 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.

III. Properties of Propylene Polymer (M) The propylene polymer (M) according to the present invention is excellent in the balance between physical properties and melt processability with controlled melt fluidity (melt spreadability) and melt tension. The physical properties of the propylene polymer (M) according to the present invention will be described.
1. Melt flow rate (MFR)
The propylene-based polymer (M) according to the present invention requires a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 kg to be 0.1 g / 10 min or more and 100 g / 10 min or less. To do.
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. Generally, when this value is small, fluidity is deteriorated and various moldings cannot be performed. Accordingly, the MFR needs to be 0.1 g / 10 min or more, preferably 0.2 g / 10 min or more, and more preferably 0.3 g / 10 min or more.
In general, 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. Accordingly, the MFR needs to be 100 g / 10 min or less, and preferably 60 g / 10 min or less.

Furthermore, the range of preferable values varies depending on the molding method used. For example, when used as a melt tension modifier, the lower limit is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more. It is. On the other hand, the upper limit is preferably 3.0 g / 10 min or less, more preferably 1.0 g / 10 min or less.
When used for extrusion foam molding, the lower limit is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more. On the other hand, the upper limit is preferably 10 g / 10 min or less, more preferably 3.0 g / 10 min or less.
When used for injection foam molding, the lower limit is preferably 1.0 g / 10 min or more, more preferably 3.0 g / 10 min or more. On the other hand, the upper limit is preferably 60 g / 10 min or less, more preferably 30 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. It can be carried out.

2. Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC
The propylene polymer (M) according to the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) as measured by gel permeation chromatography (GPC), and Mw / Mn (Q value) is 3. It is necessary to be in the range of 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, and satisfactory physical properties cannot be obtained. 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) of the propylene polymer (M) measured by GPC can be changed by changing the temperature and pressure conditions of propylene polymerization, or the most common technique is hydrogen or the like The chain transfer agent can be easily adjusted by adding the chain transfer agent during propylene polymerization. Furthermore, when using 2 or more types of the metallocene complex to be used and a complex, it can control by changing the quantity ratio.

3. Bias of molecular weight distribution obtained from GPC molecular weight distribution curve toward high molecular weight side The propylene-based polymer (M) according to the present invention has a common logarithm of molecular weight corresponding to the peak position in the molecular weight distribution curve obtained by GPC. Is Tp, 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), and α and β are respectively When α = H ₅₀ −Tp and β = Tp−L ₅₀ are defined, it is desirable that α / β is greater than 0.9 and not greater 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 homopolymer, and is different from the weight average molecular weight (Mw) of the propylene homopolymer. 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, α / β is desirably larger than 0.9 and not larger 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 homopolymer according to the present invention means that the molecular weight distribution of the propylene homopolymer that is uniformly polymerized at a single active point 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. For example, when extrusion foam molding is performed, in the stage where initial bubbles are formed, the lower the viscosity, the more the cores of the bubbles. On the other hand, in the state where the bubble cell is formed and thinned, if the portion is not strong, the bubble is broken, and thus a component having a high molecular weight is required. In order to satisfy such circumstances, it is important that the molecular weight is further spread on the high molecular weight side than on the low molecular weight side.
Therefore, the propylene polymer (M) according to the present invention desirably has an α / β ratio of greater 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 and the fluidity is deteriorated. In addition, when foam molding is performed, the viscosity is increased due to too much high molecular weight component, and there is a tendency that sufficient bubble cells cannot be formed at the initial stage of molding. Moreover, when extending | stretching at high speed at the time of shaping | molding, it will cause what is called a melt ductility deterioration that a melt will fracture | rupture.
Therefore, the propylene polymer (M) according to the present invention desirably has an α / β value of 2.0 or less, preferably 1.7 or less, and more preferably 1.6 or less.
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.
In the case of the propylene-based polymer (M), the molecular weight distribution obtained from the molecular weight distribution curve by GPC is biased toward the high molecular weight side so that a high molecular weight polymer can be produced as one of the two metallocene complexes used. After selection, it can be easily adjusted by controlling the amount of hydrogen added during 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 The propylene-based polymer (M) according to the present invention has a molecular weight (M ) Is a component having a content of 2 million or more of 0.4% by weight or more and 10% by weight or less.
The above-mentioned ratio of 2 million or more components (hereinafter referred to as W (2 million or more)) is an index indicating the ratio of very high molecular weight components contained in the polymer.
W (2 million or more), which is the ratio of the very high molecular weight component, is an integral molecular weight distribution curve obtained by GPC (the total amount is normalized to 1). = 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. For example, when performing extrusion foam molding, bubble breakage occurs and the closed cell ratio does not increase. 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 polymer (M) according to 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 Is 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. On the other hand, if the ratio of this component is too high, the melt will break when the film is stretched at a high speed during molding, so-called deterioration of melt ductility is caused.
Therefore, the propylene polymer (M) according to the present invention desirably has W (2 million or more) of 10% by weight or less, preferably less than 6.0% by weight, more preferably 5.0%. Less than% by weight.
In the case of the propylene-based polymer (M), the ratio of the component having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC is selected from those capable of producing a high molecular weight polymer as the metallocene complex to be used. Adjustment can be easily made by controlling the ratio of the metallocene complex to produce the low molecular weight side, the amount of hydrogen added during propylene polymerization, 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)
The propylene-based polymer (M) according to the present invention is, for example, a propylene homopolymer having 3.0% by weight of a component that elutes at a temperature of 40 ° C. or less in an elution curve obtained by temperature rising elution fractionation (TREF) measurement. % 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. .
The temperature rising elution fractionation (TREF) of the propylene polymer (M) with orthodichlorobenzene (ODCB) can be generally kept low by using a metallocene complex, but the purity of the catalyst is more than a certain level. In addition to maintaining the catalyst, it is necessary that the manufacturing method of the catalyst and the reaction conditions during the polymerization are not extremely high, and that the amount ratio of the organoaluminum compound to the metallocene complex is not excessively increased.

The measurement method of the elution component by temperature rising elution fractionation (TREF) is 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
The propylene polymer (M) according to 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) of the propylene polymer (M) measured by 13C-NMR can be easily adjusted by the selection of the metallocene complex described later, the polymerization temperature and the polymerization pressure.

^The method for measuring the mm fraction of three propylene units 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 such that the center peak was 74.2 ppm with three peaks of deuterated 1,1,2,2-tetrachloroethane. The chemical shifts of other carbon peaks are 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.
The spectrum was assigned with reference to Macromolecules, 8 pp. 687 (1975) and Polymer, Vol. 30, p. 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 are generated 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 is slightly shifted depending on the molecular weight and the 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)

  Further, the propylene polymer (M) according to 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, with peaks not based on the head-to-tail three-linkage. It is necessary to reduce the peak areas based on A, A ′, A ″, B, and 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 of the position irregular substructure [structure (5-b) and structure (5-c)]. 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
The propylene polymer (M) according to the present invention is required 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, for example, uneven thickness is unlikely to occur during blow molding. In addition, the closed cell ratio can be increased when foam molding is performed.
Therefore, the strain hardening degree needs to be 6.0 or more, preferably 10.0 or more, more 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, the branched chain length of the propylene polymer (M) according to the present invention is not less than 500 skeletal carbon (polypropylene molecular weight conversion: 11,000) as described above, preferably 1000 skeletal carbon (polypropylene molecular weight). Conversion: 21,000) 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 (M) according to the present invention is 11,000 or more, preferably 21,000 or more, more preferably 4.2 in terms of number average molecular weight (Mn) measured by GPC. It can be replaced with over 10,000.
The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer (M) can be determined by controlling the selection of two types of metallocene complexes constituting the catalyst used for propylene polymerization, the ratio of the amounts thereof, and the prepolymerization conditions. , 6.0 or more. 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 the measuring instrument are described in the general document 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, and the maximum value (ηmax) of the extensional viscosity η _E until the amount of strain 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)
In the propylene polymer (M) according to the present invention, the memory effect (ME) preferably satisfies the following formula (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. ]

The propylene-based polymer (M) according to the present invention preferably has a correlation between a memory effect (ME) that is an index that represents the abundance ratio of a high molecular weight component in the polymer and an MFR that is an index that represents the average molecular weight of the polymer. It has a specific relationship (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 (M) according to the present invention has a large ME in MFR match as compared with a conventionally known polymer as shown in FIG. 5 due to the presence of a branching component in the polymer chain. It is a feature. When the amount of the long-term relaxation component is large, the swell becomes large, and it is known that the generation characteristics such as flow mark during injection molding are suppressed. Excellent molding characteristics. More preferably, the following formula (I-2) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.20 (I-2)
More preferably, the following formula (I-3) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.40 (I-3)

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

9. Melt tension and melt spreadability The propylene-based polymer (M) according to the present invention has a controlled branch structure (branch amount, branch length, branch distribution), so that the 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 the 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 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 according to the present invention has improved melt tension by broadening the molecular weight distribution and introducing branches, and therefore MT is 5 g or more, preferably 10 g or more, more preferably 15 g or more. is there.

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 polymer (M) according to the present invention can have a large MaxDraw while maintaining a high MT by controlling the branching component, and the balance between melt tension and melt spreadability is improved.
Accordingly, the propylene polymer (M) according to 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.
It is important for the maximum winding speed (MaxDraw) of the propylene polymer (X) to reduce non-homogeneous components such as a gel. In order to obtain a homogeneous propylene polymer (M), diene or the like In the macromer polymerization method that does not use the catalyst, the prepolymerization conditions of the catalyst used and the polymerization conditions such as the hydrogen concentration and temperature can be controlled.

As described above, the propylene-based polymer (M) according to 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 workability. In contrast to conventional propylene-based polymers, for example, as described above, JP-A-2007-154121 discloses propylene homopolymers having a branch number of 0.1 / 1000 skeleton carbon or more. The strain hardening degree (λmax) in the measurement of viscosity is less than 6.0, and the strain hardening degree (λmax) in the measurement of the extension viscosity of the propylene polymer (M) according to 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. The isotactic triad fraction (mm) by ¹³ C-NMR is low (92.5%), and it is considered that molecular cleavage and isomerization occur simultaneously with crosslinking upon irradiation with an electron beam. Solvent-soluble components also occur and low molecular weight components are increasing. In addition, as another general method for controlling the molding processing 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, resulting in molding. Demerits such as deterioration of the surface characteristics of the body, a fixed price of mechanical properties and a decrease in heat sealability occur.
However, the propylene-based polymer (M) according to 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 is increased. Since the components increase, the above disadvantages do not occur.
Thus, since the propylene polymer (M) according to the present invention is a long-chain branched type, the physical properties and processability are controlled by controlling the melt ductility and melt tension not found in conventional propylene polymers. It has become an excellent balance.

IV. Production method of propylene polymer (M) About the method of producing the propylene polymer (M) according to the present invention, the physical properties and processability are controlled by the above-described melt ductility and melt tension, which are the features of the present invention. There is no particular limitation as long as it is a method capable of obtaining a long-chain branched propylene-based polymer having an excellent balance, but, for example, as a method for introducing a controlled branched component, a plurality of complexes as described below are used. A method can be mentioned.
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.
(A): at least one from component [A-1] which is a compound represented by the following general formula (a1) and at least one from component [A-2] which is a compound represented by general formula (a2) Two or more types of transition metal compounds selected from Group 4 of the periodic table Component [A-1]: Compound represented by general formula (a1) Component [A-2]: Represented by general formula (a2) Compound (B): Ion exchange layered silicate (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. 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. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

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}] hafniu , Dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5 -Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-diphenylsilylenebis {2- (5-methyl-2-furyl)- -Phenyl-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-tert-butylphenyl) -indenyl}] Hough Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2- Furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [ 1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2- Furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2- Butyl) -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-tert-butyl-2-furyl) -4- (2-naphthyl) -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] ha Nitrogen, 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- (2-naphthyl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {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- (2-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), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, sulfur. , Nitrogen, boron, phosphorus, or a C6-C16 aryl group that may contain 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 in this invention refers to the silicate of the previous step which performs the chemical processing based on 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 smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and 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 may be any of a surface treatment for removing 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, but usually the salt and acid concentrations are selected from 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchanged layered silicate is eluted. 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. Moreover, the combination of these acids and salts may be sufficient.

<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>:
As examples of the organic treatment agent used in the organic substance treatment, 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 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 component (B) after removal is 3% by weight or less, preferably 0% by weight when the water content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. Is preferably 1% by weight or less.

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

  The ion-exchange layered silicate can be treated with the component (C) described later before formation of the catalyst or use as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of the 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 component (B) is preferably a spherical particle 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. As the organoaluminum compound used as the component (C), a compound represented by the general formula: (AlR ¹¹ _q Z _3-q ) _p is appropriate.
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 a (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 using component (C), before contacting component (A) with component (B), component (A), or component (B), or both component (A) and component (B) The component (C) is contacted, or the component (A) and the component (B) are contacted at the same time as the component (C) is contacted, or the component (A) and the component (B) are contacted. Although it is possible to contact the component (C) later, a method of contacting the component (C) with any of the components (A) and the component (B) is preferable.
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of component (A) used relative to 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 component (B). The amount of component (C) used relative to component (B) is preferably such that the amount of Al is 0.01 to 1000 mmol, particularly preferably 0.05 to 500 mmol, relative to 1 g of component (B). Therefore, the amount of the component (C) to the component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ 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 (M) is satisfy | filled, component [A-1] and component [A] -2] is preferably a molar ratio of the transition metal of component [A-1] to the total amount of 0.30 or more and 0.99 or less.
By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body 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. Transition of component [A-1] with respect to the total amount of component [A-1] and component [A-2] in order to produce a propylene polymer having a higher degree of strain hardening efficiently with higher catalytic activity The molar ratio of the metal needs to be 0.30 or more, preferably 0.40 or more, and more preferably 0.50 or more. Further, the upper limit is 0.99 or less, and in order to efficiently obtain the propylene polymer (M) according to the present invention with high catalytic activity, it is preferably 0.95 or less, more preferably 0. .90 or less.
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen.

  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 physical 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 Any polymerization method may be used as long as the olefin polymerization catalyst including the component (A), the component (B) and the component (C) is in efficient contact with the monomer. sell.
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. A method of performing continuous polymerization or batch 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, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.

Further, as a molecular weight regulator and for an activity improving effect, hydrogen is supplementarily used in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene. it can.
Moreover, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

In addition to the propylene monomer, copolymerization using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer may be performed. 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 (M) according to the present invention in a good balance between melt properties and catalytic activity, it is preferable to use ethylene at 5 mol% or less. In particular, in order to obtain a polymer having high rigidity, it is preferable to use ethylene so that ethylene contained in the polymer is 1 mol% or less, more preferably propylene homopolymerization.

(6) Consideration of Polymerization Mechanism Macromer formation is considered to be 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 relatively In the 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 higher than that of the complex having the conventional structure. Bigger than that.
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 Manufacture is possible under (40 degreeC-80 degreeC).

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 Such a propylene-based polymer (M) production method is characterized by a small change in the balance between macromer formation and growth reaction even when hydrogen is added, and it is found that the selectivity of the macromer does not change even in the presence of hydrogen. It was. 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:
Conventionally, the branching efficiency has increased only under conditions that produce a polymer with low stereoregularity, but in the method according to the present invention, a sufficiently high stereoregularity component can be added to the side chain by a simple method. It became possible to introduce. This is an important advance as an industrial manufacturing technique.

In addition, the propylene polymer (M) according to the present invention is a known antioxidant, ultraviolet absorber, antistatic agent, nucleating agent, lubricant, flame retardant, antiblocking agent, colorant, if necessary. After blending various additives such as inorganic or organic fillers and various synthetic resins, it can be used for molding materials as pellets cut into granules after heating and melt-kneading using a melt-kneader. It is.
These pellet-shaped molding materials are molded by various known polypropylene molding methods, such as injection molding, extrusion molding, foam molding, hollow molding, and various industrial injection molded parts, various containers, unstretched films. Various molded products such as a uniaxially stretched film, a biaxially stretched film, a sheet, a pipe, and a fiber can be produced.

V. Homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less [hereinafter referred to as component (H)]
In the present invention, the homopolypropylene or the ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less satisfies the requirements defined in the following (vii) to (ix).
(Vii) The isotactic pentad fraction is 95% or more. (Viii) The homopolypropylene or ethylene-propylene copolymer (H) has a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000.
(Ix) MFR (230 ° C., 2.16 kg load) is 10 to 100 g / 10 min.
Hereinafter, each characteristic will be described.

(Vii) The isotactic pentad fraction (mmmm) is 95% or more.
Here, the isotactic pentad fraction (mmmm) is A.I. It is an isotactic fraction in pentad units in a polypropylene molecular chain, as measured by ¹³ C-NMR, proposed by (A. Zambelli) ((Macromolecules 6, 925 (1973)). The method for determining the attribution of the peak in the measurement is determined according to the attribution proposed by A. Zamberg et al. (Macromolecules, Vol. 8, page 687 (1975)).
The measuring method of ¹³ C-NMR spectrum is as follows. 100-500 mg of sample is completely dissolved using about 2.2 ml of orthodichlorobenzene in a 10 mm NMR sample tube. Next, about 0.2 ml of deuterium benzene is added and homogenized as a lock solvent, and measurement is performed at 130 ° C. by a proton complete decoupling method. The measurement conditions are a flip angle of 90 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value of the spin-lattice relaxation time of the methyl group). Since the spin lattice relaxation time of methylene group and methylene group is shorter than that of methyl group in the propylene polymer, the recovery of the magnetization of all carbons is 99% or more under this measurement condition. ^{As a 13} C-NMR measuring apparatus, INOVA500 manufactured by Varian was used.

(Viii) Homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less has a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000.
As the component (H), those having a weight average molecular weight in the range of 100,000 to 1,000,000 are used.
The weight average molecular weight (Mw) is measured by a GPC measuring apparatus and conditions described later, and it is necessary that the Mw of the component (H) is in the range of 100,000 to 1,000,000. When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.

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

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

(Ix) MFR (230 ° C., 2.16 kg load) is 10 to 100 g / 10 min.
The MFR of component (H) is 10 to 100 g / 10 minutes, preferably 20 to 40 g / 10 minutes. When the MFR is 10 g / 10 min or less, the viscosity is increased due to too little high molecular weight component, and the flowability during injection molding is deteriorated. On the other hand, if the MFR exceeds 100 g / 10 min, an increase in the plasticizing time due to slipping or poor dispersion of the pigment MB due to insufficient shearing tends to occur.
In order to adjust the MFR of the polymer, for example, there are a method of appropriately adjusting a polymerization temperature, a catalyst amount, a supply amount of hydrogen as a molecular weight regulator, or a method of adjusting by adding a peroxide after completion of polymerization. .
Here, MFR is a value measured according to JIS K6921 at a heating temperature of 230 ° C. and a load of 2.16 kg.

VI. Method for producing homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less Component (H) used in the present invention may be obtained by any method. . Generally, propylene or propylene and other α-olefins are polymerized in the presence of a co-catalyst such as triethylaluminum or diethylaluminum using a Ziegler-Natta type catalyst or a magnesium chloride supported Ziegler-Natta catalyst. Can be obtained by:

Also, a Kaminsky catalyst using a metallocene compound can be used. As the metallocene compound used for the Kaminsky catalyst, an organic transition metal compound comprising a group 4-6 transition metal compound, particularly a group 4 transition metal compound such as Zr, Ti, Hf and the like, and cyclopentadiene or a cyclopentadiene derivative is used. Can be used.

As the cyclopentadiene derivative, an alkyl substituent such as pentamethylcyclopentadiene or a compound in which two or more substituents are combined to form a saturated or unsaturated cyclic substituent can be used. Fluorene, azulene, or a partial hydrogenated product thereof. A compound in which a plurality of cyclopentadiene is bonded by an alkylene group, a silylene group, a germylene group, or the like can also be used.
As the co-catalyst, a compound that reacts with an organoaluminum or metallocene catalyst to become a stable ion can be used. Generally, an alumoxane, an ion-exchange silicate compound, or the like is used.

Specific methods for producing the component (H) using a metallocene catalyst are disclosed in JP-A-58-19309, JP-A-60-35007, JP-A-3-163088, European Patent Application Publication No. 420, 436, US Pat. No. 5,055,438, and International Publication No. WO09 / 04257, for example, metallocene catalysts, metallocene / alumoxane catalysts, or, for example, International Publications Examples thereof include a polymerization method using a catalyst comprising a compound that reacts with a metallocene compound and a metallocene catalyst as disclosed in W092 / 07123 and the like to form a stable ion.
As a polymerization method, a slurry method in the presence of these catalysts, a gas phase fluidized bed method (for example, a method described in JP-A-59-23011), a solution method, or a pressure of 200 kg / cm ² or more, A high-pressure bulk polymerization method or the like at a polymerization temperature of 100 ° C. or higher can be employed.

VII. Propylene-based resin composition To the propylene-based resin composition of the present invention, other synthetic resins and nucleating agents can be added within a range not impairing the object of the present invention. Examples of other synthetic resins include ethylene, butene -1, pentene-1, 4-methylpentene-1, etc., homopolymers of α-olefins, or copolymers thereof can be used. In this case, the synthetic resin to be added is blended in an amount of 30 parts by weight or less, preferably 20 parts by weight or less based on 100 parts by weight of polypropylene.

  In the present invention, known nucleating agents can be used, specifically, aluminum benzoate, potassium benzoate, sodium benzoate, lithium benzoate, aluminum-p-butylbenzoate, β-sodium naphthoate, cyclohexane. Carboxylic acid metal salt compounds such as sodium carboxylate and sodium cyclopentanecarboxylate; sodium bis (4-t-butylphenyl) phosphate, lithium bis (4-t-butylphenyl) phosphate, bis (4- t-butylphenyl) aluminum phosphate, bis (4-t-butylphenyl) calcium phosphate, bis (4-t-butylphenyl) magnesium phosphate, 2,2′-methylene-bis (4,6-di) -T-butylphenyl) phosphate sodium salt, 2,2'-methylene-bis (4,6-di-) -Butylphenyl) lithium phosphate, 2,2'-methylene-bis (4,6-di-t-butylphenyl) aluminum phosphate, 2,2'-methylidene-bis (4,6-di-t) -Butylphenyl) calcium phosphate, 2,2'-methylidene-bis (4,6-di-t-butylphenyl) magnesium phosphate, 2,2'-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate sodium salt, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate lithium, 2,2′-ethylidene-bis (4,6-di-t-butyl) Aromatic metal phosphate compounds such as phenyl) aluminum phosphate; dibenzylidene sorbitol, 1,3,2,4-di (methylbenzylidene) sorbitol, 1,3,2,4-di (ethylbenzylidene) Sorbitol, 1,3,2,4-di (butylbenzylidene) sorbitol, 1,3,2,4-di (methoxybenzylidene) sorbitol, 1,3,2,4-di (ethoxybenzylidene) sorbitol, 1,3 -Dibenzylidene sorbitol compounds such as chlorobenzylidene, 2,4-methylbenzylidene sorbitol, mono (methyl) dibenzylidene sorbitol; inorganic compounds such as silica, titanium dioxide, carbon black, talc, mica, alum and pigment . Of these, aluminum-p-butylbenzoate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate metal salt and 1,3,2,4-di (methylbenzylidene) sorbitol are preferable. .

  In the present invention, the nucleating agent is blended in an amount of 0.01 to 3.0 parts by weight, preferably 0.03 to 1.0 parts by weight, based on 100 parts by weight of the propylene-based resin composition. If the nucleating agent is less than 0.01 part by weight, the expression of rigidity is insufficient, and if it exceeds 3.0 parts by weight, the improvement of the effect is reduced. Said nucleating agent may be used individually by 1 type, or may use 2 or more types together.

  In addition to the above components, the propylene-based resin composition of the present invention can contain an inorganic filler such as titanium oxide, clay, barium sulfate, calcium carbonate, preferably barium sulfate. The blending ratio of the inorganic filler is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of polypropylene, and more preferably about 0.5 to 20 parts by weight. Moreover, various additives can be further mix | blended with a propylene-type resin composition in the grade which does not impair the effect of invention.

  Specific additives include phenolic, organic phosphite, phosphonite and other organic phosphorus, thioether and other antioxidants; hindered amines and other light stabilizers; benzophenone, benzotriazole, benzoate, etc. UV absorbers; nonionic, cationic, anionic and other antistatic agents; bisamides, waxes, organometallic salt-based dispersants; alkaline earth metal carboxylate-based chlorine scavengers; amides Lubricants such as organic metal salts and esters; metal deactivators such as hydrazine and amine acids; flame retardants such as bromine-containing organic, phosphoric acid, antimony trioxide, magnesium hydroxide and red phosphorus; organic Examples thereof include pigments; inorganic pigments; foaming agents; inorganic and organic antibacterial agents such as metal ions.

  In the present invention, each of the above components can be blended by an ordinary method. For example, a nucleating agent and, if necessary, other additives are added to polypropylene and mixed with a tumbler or a Henschel mixer. Then, a method of melt kneading and pelletizing with an extruder can be used.

VIII. Food containers and medical members using the propylene-based resin composition The propylene-based resin composition thus obtained is molded into various products by molding methods such as injection molding, blow molding, and press molding.
As the molding method, an injection molding method is preferable. This injection molding can adopt techniques such as a gas assist injection method, a melt core molding method, an insert molding method, a two-color molding method, a foam molding method, and an injection compression molding method.
Thereby, a food container and a medical member are shape | molded easily. The propylene resin composition of the present invention is a specific amount of propylene polymer (M) as a modifier to homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less. Since it is added, the flow mark of the component M is improved while maintaining the fluidity of the component H, which is advantageous for forming a baked pudding container or a medical instrument that requires heat treatment.

  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) 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 measured by said method 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:
Measurement was performed by the above method using JSX-GSX-400, FT-NMR. The unit is%.
(5) mmmm fraction:
Measurement was performed using a 270 MHz apparatus using GSX-400, FT-NMR, manufactured by JEOL Ltd.
(6) Measurement of ethylene content:
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.
(7) Elongation viscosity:
It was measured by the method described in the present specification.

(8) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.
(9) 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.).
(10) Deflection temperature under load (HDT, unit: ° C)
In accordance with JIS K7207 “Method for testing temperature of deflection of hard plastic under load”, the measurement was performed with an Automatic Heat Distortion Tester under a load of 4.6 kgf / cm ² .

[Synthesis Example 1 of Catalyst Component (A)] (Complex 1):
(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)] (Complex 2):
(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)] (Complex 3):
(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.

[Catalyst Synthesis Example 1 for Propylene Polymer (M)] (Preliminary Polymerization Catalyst 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:
Into 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, to which was added a triisobutylaluminum (25 mmol: heptane solution having a concentration of 143 mg / mL). 6 mL) and stirred for 1 hour, washed with heptane to a residual liquid ratio of 1/100, and heptane was added so that the total volume became 100 mL.
Further, in another flask (volume: 200 mL), the complex 1: rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-) prepared in Synthesis Example 1 of the catalyst component (A) was prepared. Furyl) -4- (4-t-butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (Solution 1), and in another flask (volume 200 mL), the catalyst component (A ) Complex 3 prepared in Synthesis Example 3: rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (45 μmol) 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 27.5 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.75 (preliminary polymerization catalyst 1).

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

  The molecular weight of the prepolymerized polymer of the prepolymerized catalyst obtained above was measured using GPC. The weight average molecular weight and Q value are shown in Table 1.

[Propylene Polymer (M) (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), 250 Nml of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 90 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 3 hours, 5 ml of ethanol was injected to stop the polymerization. As a result, 409 g of a polymer was obtained.
5 g of the obtained polymer was dissolved in hot xylene and then precipitated with a large amount of ethanol. After filtration, it was dried under reduced pressure to obtain a sample for analysis.
Table 2 shows the evaluation results of the obtained polymer samples.

[Propylene Polymer (M) (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. 2.86 mL of a heptane solution of triisobutylaluminum (143 mg / mL) was added, and 450 Nml of hydrogen was introduced. Next, after introducing 750 g of liquid propylene, the temperature was raised to 70 ° C.
Thereafter, 100 mg of the prepolymerized catalyst 2 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon, and polymerization was started. After maintaining at 70 ° C. for 1 hour, 5 ml of ethanol was injected to stop the polymerization. As a result, 315 g of a polymer was obtained.
Table 2 shows the evaluation results of the obtained polymer samples.

[Comparative propylene polymer (polymerization example 3)]:
This polymerization example 3 was carried out according to Example 29 described in JP-A-2002-523575.
In a 1 L autoclave thoroughly purged with nitrogen, 500 ml of heptane, 2.5 ml of MMAO, 2.5 ml of MMAO and 1 ml of a toluene solution of dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride (1 mg / ml) were added. What was activated by contact was introduced and kept at 50 ° C. Propylene was slowly introduced, and finally polymerization was carried out for 1 hour while maintaining the pressure in the polymerization tank at 0.5 MPa. After completion of the polymerization, the polymer was collected by filtration and dried under reduced pressure to obtain 35 g of polymer.
Table 2 shows the evaluation results of the obtained polymer samples.

  Comparative Polymerization Example 3 is different from Polymerization Examples 1 and 2 of the present invention in that the catalyst used and the polymerization conditions are different, so that the resulting polymer has a small amount of branching and strain hardening is small. Moreover, since there is no spread of molecular weight distribution to the high molecular weight side, there is a drawback that it is not suitable for foam molding.

[Homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less (polymerization example 4)]:
(1) Synthesis of solid catalyst component (A) A 30 L autoclave equipped with a stirrer, a pressure gauge and a thermometer and substituted with high-purity nitrogen was added with 2.3 kg of magnesium ethoxide and 4.15 L of 2-ethyl-1-hexanol. And 16.5 L of toluene were added. This mixture was heated to 90 ° C. in a carbon dioxide gas atmosphere of 0.2 MPa (hereinafter referred to as gauge pressure), and stirred at a rotational speed of 150 rpm for 3 hours. The obtained solution was cooled and carbon dioxide gas was deaerated to obtain a solution (a). This solution contained 0.1 g / L of magnesium ethoxide. Into a 15 L autoclave (baffle rate 0.15) equipped with a stirrer, thermometer, condenser, nitrogen seal line and baffle, 3 L of toluene, TiCl ₄ (190 ml) and 250 ml of hexamethyldisiloxane were charged and rotated at room temperature. After mixing at several 250 rpm for 5 minutes, 1.5 L of the solution (a) was added in 10 minutes. Immediately after the addition, solid particles (I) were precipitated.
30 ml of ethanol and 0.5 L of tetrahydrofuran (THF) were added to the solution containing the solid particles (I), and the temperature was raised to 60 ° C. within 15 minutes while maintaining stirring at a rotation speed of 150 rpm. (I) dissolved and then solid particles began to precipitate again within 15 minutes. The formation of the solid particles was completed within 10 minutes. Further, the stirring was continued for 45 minutes at 60 ° C., and then the stirring was stopped to precipitate the produced solid (II).
The supernatant was removed by decantation and the remaining product solid (II) was washed twice with 2 L of toluene. To the resulting solid (II), 2 L of toluene and TiCl ₄ (1 L) were added, and the temperature was raised to 135 ° C. within 20 minutes while stirring at a rotation speed of 250 rpm, and this temperature was maintained for 1 hour. Stirring was stopped, the resulting solid (III) was allowed to settle, and the supernatant was removed by decantation.
TiCl ₄ (1 L), toluene 2.5 L, and 21 ml of diisobutyl phthalate were added to the resulting solid (III), heated to 135 ° C., and stirred for 1.5 hours at a rotational speed of 250 rpm. The supernatant was removed by decantation, and TiCl ₄ (2 L) was added to the residue and refluxed for 10 minutes with stirring. The supernatant was removed by decantation, and the residue was washed 3 times with 2 L of toluene and 4 times with 2 L of hexane to obtain 116 g of a solid catalyst component (A). This solid catalyst component (A) contained 17.3% by weight of magnesium, 2.3% by weight of titanium, 55.6% by weight of chlorine, and 8.6% by weight of diisobutyl phthalate.

(2) Prepolymerization treatment A stainless steel reactor equipped with a stirrer and purged with high-purity nitrogen was charged with 20 L of hexane, 100 g of the solid catalyst component (A), 0.1 mol of triethylaluminum and diisopropyldimethoxysilane. 015 mol was added. While stirring at 30 ° C. and a rotation speed of 200 rpm, propylene gas was introduced and pressurized until the propylene partial pressure became 0.1 MPa, and a prepolymerization treatment was performed for 6 hours. Thereafter, propylene gas was purged. The amount of polymerized propylene was 3 g with respect to 1 g of the solid catalyst component (A).

(3) Main polymerization A 100 L stainless steel reactor equipped with a stirrer and substituted with high-purity nitrogen was preliminarily polymerized at 0.5 g / h with the solid catalyst component (A) as a solid catalyst component, and triethyl Aluminum was continuously supplied at 0.018 mol / h and diisopropyldimethoxysilane at 0.003 mol / h. At the same time, propylene is continuously supplied under the condition of a polymerization temperature of 70 ° C. so that the polymerization pressure is maintained at 2.3 MPa, and further hydrogen is added so that the hydrogen / propylene molar ratio in the gas phase becomes 0.055. Continuously supplied, propylene was continuously vapor-phase polymerized, and powdery polypropylene was obtained at a production rate of 14 kg / h.

(4) Granulation For 100 parts by weight of the obtained powdered polypropylene, the antioxidant tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] 0.10 parts by weight of methane, 0.10 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H- Dibenzo [d, g] [1,2,3] dioxaphosphocin-6-oxide) A mixture of an aluminum hydroxide salt and an organic compound (2000 ppm) was added and mixed uniformly with a Henschel mixer (trade name). The obtained mixture was melt-kneaded at an extrusion temperature of 230 ° C. using an extruder having a diameter of 65 mm and an L / D of 30 to obtain pellet-shaped homopolypropylene (H).
The polymer sample had an MFR of 20.6 dg / min, a Tm of 163.4 ° C., and an ME of 1.22. The isotactic pentad fraction (mmmm) was 97%.

(Examples 1-4, Comparative Examples 1 and 2)
5% by weight or 10% by weight of the propylene polymer (M) obtained in Polymerization Example 1 or 2 and 90% by weight or 95% by weight of the homopolypropylene (H) obtained in Polymerization Example 4 were mixed, The propylene resin composition of the invention was prepared. A propylene resin for comparison was prepared by mixing 5% by weight or 10% by weight of the propylene polymer obtained in Polymerization Example 3 and 90% by weight or 95% by weight of the homopolypropylene (H) obtained in Polymerization Example 4. A composition was prepared. The evaluation results are shown in Table 3.

The propylene-based polymer (M) according to the present invention has good flow characteristics, high melt tension, high swell ratio, high melt ductility, and excellent molding processability. It can be widely used in various molded products such as various industrial injection molded parts, various containers, unstretched films, uniaxially stretched films, biaxially stretched films, sheets, pipes, and fibers.
Moreover, the propylene-based resin composition of the present invention has characteristics such as heat resistance and high rigidity, and further has good flow characteristics and can improve moldability.
In particular, the flow of component H by adding propylene polymer (M) as a modifier to homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less. The improvement effect of the flow mark by the component M can be expected while maintaining the properties, and because of their excellent properties, it is suitably used for various molded products obtained by injection molding, thermoforming, especially food containers and medical members. be able to. It is particularly suitable for baked pudding containers or medical instruments that require heat treatment. Further, because of these excellent properties, it is excellent in moldability and can be suitably used for foam molding, sheet molding, blow molding and the like.

Claims (9)

Propylene resin composition comprising 1 to 50% by weight of propylene polymer (M) and 50 to 99% by weight of homopolypropylene or ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less A thing,
The propylene polymer (M) satisfies the requirements defined in the following (i) to (vi), and homopolypropylene or an ethylene-propylene copolymer (H) having an ethylene content of 0.5% by weight or less is The propylene-based resin composition satisfying the requirements specified in (vii) to (ix) below.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.1 g / 10 min or more and 100 g / 10 min or less,
(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,
(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 10 wt% or less,
(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,
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more,
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.
(Vii) the isotactic pentad fraction is 95% or more,
(Viii) Homopolypropylene or ethylene-propylene copolymer (H) has a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000,
(Ix) MFR (230 ° C., 2.16 kg load) is 10 to 100 g / 10 min. Furthermore, the requirements prescribed | regulated to following (x) are satisfy | filled, The propylene-type resin composition of Claim 1 characterized by the above-mentioned.
(X) (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 (M) satisfies the requirements specified in the following (xi).
(Xi) 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 that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, 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 and 2 0.0 or less.   A food container formed by molding the propylene-based resin composition according to any one of claims 1 to 3.   The food container according to claim 4, wherein the propylene-based resin composition is injection-molded.   The food container according to claim 4 or 5, wherein the thickness is 0.2 to 2.0 mm.   A medical member obtained by molding the propylene-based resin composition according to any one of claims 1 to 3.   The medical member according to claim 7, wherein the propylene-based resin composition is injection-molded.   Thickness is 0.2-2.0 mm, The medical member of Claim 7 or 8 characterized by the above-mentioned.

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