JP5286147B2 - Polypropylene deep-drawn body - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a polypropylene-based deep-drawn molded body, and more specifically, a polypropylene-based deep-drawing that is obtained by solid-phase pressure molding a polypropylene-based sheet at a temperature below the melting point, has excellent rigidity and transparency, and has less uneven thickness. It relates to a molded body.

Thermoplastic resins such as polystyrene, polyethylene terephthalate, and polypropylene are used as materials for various containers. Such a container can be obtained by extruding a thermoplastic resin into a sheet and then reheating it and performing secondary processing using a thermoforming method such as vacuum forming or vacuum / pressure forming. Such a thermoforming method is widely used as a molding method suitable for mass production because of its high productivity and easy multilayering.
Among thermoplastic resins, propylene-based polymers are excellent in heat resistance, rigidity, impact resistance, or hygiene, and thus are suitably used as containers for foods, and in particular, have high heat resistance. The range of use is expanding to range-up containers in necessary microwave ovens, containers that require high-temperature filling, and the like.

  On the other hand, in recent years, deep-drawn containers such as one-hand cups (containers with a large depth / caliber ratio) have been manufactured by the thermoforming method. Further, such containers are required to have transparency and high-grade gloss that allow the contents to be easily seen, and development of a sheet that can be formed into a container having such characteristics is required.

  However, in order to perform deep drawing, a molding temperature higher than the normal molding temperature is required. However, when a propylene-based resin used in a conventional thermoforming method is used, the moldability is remarkably reduced. However, there is a problem that transparency and gloss are lowered.

Therefore, in order to improve transparency and gloss, a method using an endless belt with a propylene polymer added with a nucleating agent at a melting point or higher (see, for example, Patent Document 1), or a random polypropylene and a nucleating agent for homopolypropylene. In this method, although the transparency and gloss of the sheet are good, the obtained sheet is subjected to secondary drawing by deep drawing. When processed, there is a problem that transparency and gloss are lost during the processing, and the expected effect cannot be obtained.
In addition, a method using syndiotactic polypropylene for the surface layer (for example, see Patent Document 3) and a method using a cyclic polyolefin (for example, see Patent Document 4) have also been proposed, but these have high material costs. There is a drawback of becoming.
Under these circumstances, there is a need for an early development of a polypropylene-based deep-drawn molded product that eliminates the problems of propylene-based resins used in conventional thermoforming methods, has excellent rigidity and transparency, and has less uneven thickness. Yes.

Japanese Patent Laid-Open No. 10-1548 JP-A-7-148853 JP-A-7-32557 JP-A-9-1750

  In view of the problems of the prior art, an object of the present invention is a polypropylene-based deep-drawing molding that is obtained by solid-phase pressure molding of a polypropylene-based sheet at a temperature below the melting point and has excellent rigidity and transparency, and less uneven thickness. To provide a body.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a solid phase pressure molding of a sheet made of a propylene resin composition containing a specific propylene polymer at a temperature below the melting point. The resulting polypropylene-based deep-drawn molded article has little uneven thickness and is excellent in transparency and gloss, and has completed the present invention.

That is, according to the first invention of the present invention, 3 to 100% by weight of the propylene polymer (X) satisfying the following requirements (i) to (vi) and 0 to 97% by weight of the propylene polymer (Y). % Of a haze value of 5% or less and a gloss value of 120% or more obtained by solid-phase pressure molding a sheet comprising a propylene-based resin composition containing a polymer mixture of A deep-drawn molded article having a uniform thickness and a depth / caliber of 1 or more times is provided.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.

According to a second invention of the present invention, in the first invention, the propylene-based resin composition contains 0.01 to 1 part by weight of a crystal nucleating agent with respect to 100 parts by weight of the polymer mixture. A polypropylene deep-drawn article according to claim 1 is provided.
According to a third invention of the present invention, in the second invention, the crystal nucleating agent is an aromatic carboxylic acid metal salt, an aromatic phosphate metal salt, a sorbitol derivative, an amide nucleating agent, or rosin. There is provided a polypropylene-based deep-drawn molded article characterized by being at least one selected from metal salts.

According to the fourth invention of the present invention, in any one of the first to third inventions, the propylene polymer (X) further satisfies the following requirement (vii): A deep drawn compact is provided.
Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]
According to a fifth invention of the present invention, in any one of the first to fourth inventions, the propylene polymer (X) further satisfies the following requirement (viii): A deep drawn compact is provided.
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, the propylene-based polymer (Y) is polymerized using a metallocene catalyst, and has the following characteristics (i ) To (iv) are satisfied, and a polypropylene-based deep-drawn molded article is provided.
Characteristic (i): MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g / 10 min.
Characteristic (ii): Melting peak temperature (Tm) measured by DSC method is 120-165 ° C.
Characteristic (iii): Molecular weight distribution (Q value: Mw / Mn) measured by GPC method is 1.5 to 4.5.
Characteristic (iv): In an elution curve obtained by temperature rising elution fractionation (TREF), a difference (T ₈₀ -T ₂₀ ) between a temperature at which 20% by weight is extracted (T ₂₀ ) and a temperature at which 80% by weight is extracted (T ₈₀ ) ) Is 10 ° C. or lower.

  Furthermore, according to the seventh invention of the present invention, in any one of the first to sixth inventions, the polymer mixture comprises 5 to 90% by weight of a propylene polymer (X) and a propylene polymer (Y And 10 to 95% by weight of a polypropylene-based deep-drawn molded article.

  Since the polypropylene-based deep-drawn molded article of the present invention has little unevenness and is excellent in rigidity, transparency and glossiness, it can be used for containers in various fields such as food containers, detergent containers, and medical containers. In particular, it can be widely used in the beverage food field where the contents can be confirmed.

It is a figure which shows an example of the molecular weight distribution curve in GPC of the propylene-type polymer (X) based on this invention. 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 of the propylene-type polymer (X) which concerns on this invention, and [A-2]. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer. It is a figure explaining the correlation of ME (memory effect) and MFR of propylene polymer (X) concerning the present invention.

The polypropylene-based deep-drawn molded article of the present invention includes the following requirements (i) to (vi), or in addition to the requirements (vii) and / or (viii), or in addition to the requirements (ix) ) And / or (x) propylene-based resin comprising a polymer mixture of propylene-based polymer (X) 3 to 100% by weight and propylene-based polymer (Y) 0 to 97% by weight having the properties and properties shown in (x) The sheet obtained from the composition is obtained by solid-phase pressure molding at a temperature below the melting point, and the haze value is 5% or less and the gloss value is 120% or more, and the wall thickness is uniform. In addition, the depth / caliber is one or more times.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.

Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ Is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 , Less than 2.0.

Requirement (ix): MT 230 ° C. (melt tension) satisfies the following relational expression.
(MT230 ° C) ≧ 5g
[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. ]
Requirement (x): MaxDraw (maximum winding speed) satisfies the following relational expression.
(MaxDraw) ≧ 10 m / min [where, MaxDraw (maximum winding speed) represents the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. ]
Hereinafter, the constituent components of the propylene-based resin composition used for the production of the polypropylene-based deep-drawn molded product of the present invention, the method for preparing the propylene-based resin composition, the deep-drawn thermoformed product obtained therefrom, the production method thereof, etc. are described in detail. Explained.

I. Components of propylene-based resin composition Propylene polymer (X)
The propylene-based polymer (X) constituting the propylene-based resin composition used for the polypropylene-based deep-drawn molded article of the present invention is the above-mentioned requirements (i) to (vi), or in addition to these requirements (vii) And (viii), or in addition to them, the characteristics and properties shown in the requirements (ix) and / or (x).
Hereinafter, each item will be described sequentially.

(1) Structure of propylene polymer (X), definition of long chain branched structure and identification method The propylene polymer (X) according to the present invention has physical properties and melt processability with controlled melt fluidity and melt tension. It is a long-chain branched propylene polymer having an excellent balance.
It is considered that the propylene-based polymer (X) according to the present invention has a marked improvement in melt properties due to the introduction of the long chain branching.
In general, ¹³ C-NMR is used for detection and quantification of 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 requires a long time measurement or has a limit of quantification. At present, rheological methods are considered to have the highest sensitivity as a method for evaluating branching. For example, measurement of flow activation energy in linear viscoelasticity measurement and strain hardening degree in elongational viscosity measurement are generally used at this stage as a method for detecting a small amount of branching.
Regarding the branched structure, the present inventors have inferred as follows in consideration of the mechanism and mechanism capable of long-chain branching.

That is, from the active species derived from the catalyst component [A-1] used in the method for producing the propylene-based polymer (X) described later, the polymer one end is mainly formed by a special chain transfer reaction generally called β-methyl elimination. It exhibits a propenyl structure and produces a so-called macromer.
The terminal propenyl structure terminated by the β-methyl elimination reaction is shown below (Reference: Macromol. Rapid Commun. 2000, 21, 1103-1107).

It is speculated that this macromer is capable of producing a higher molecular weight and is taken in by the active species derived from the catalyst component [A-2] having a better copolymerization property, and the macromer copolymerization is proceeding.
Therefore, the propylene polymer (X) 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, page 1738).

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

As a result of ¹³ C-NMR measurement, the propylene-based polymer (X) showing improved melt properties of the present invention has a small 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 in the case of using the current ¹³ C-NMR of high magnetic field NMR, it is difficult to determine with a small amount of about 0.1 unless measurement is performed for a very long time. 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.

In addition, the propylene polymer (X) according to the present invention needs to have a branching length of 7000 or more, which is an entangled molecular weight of polypropylene. 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.
Therefore, the branched chain length of the propylene-based polymer (X) 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 (X) 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. Replaced with more than 10,000.

Further, when considering the polymerization mechanism, the macromer generated from the active species derived from the catalyst component [A-1] is incorporated into the main chain to form a branched structure, so that the average molecular weight of the macromer is that of the incorporated branched chain. Characterized as average molecular weight.
For example, in the propylene-based polymer (X) 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. Considered that long chain branching is introduced into the molecular weight component derived from [A-2] because it is considered that branching is generated by incorporation into the active species derived from component [A-2]. ing.
Since the molecular weight component derived from the catalyst component [A-2] is higher in molecular weight than the molecular weight component derived from [A-1], the branched distribution is 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 in the measurement of the extensional viscosity of the disclosed propylene homopolymer is less than 6.0, and the strain hardening degree (λmax in the measurement of the extensional viscosity of the propylene-based polymer (X) according to the present invention). ) 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 (X) according to the present invention does not necessarily have a larger number of branches (average value) than a conventional branched polymer, but by combining a plurality of complexes, branching can be 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.

(2) Physical Properties of Propylene Polymer (X) The propylene polymer (X) according to the present invention has an excellent balance between physical properties and melt processability with controlled melt fluidity and melt tension. The physical properties of the propylene polymer (X) will be described.

(2-1) Melt flow rate (MFR):
As shown in the requirement (i), the propylene polymer (X) according to the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 Kg of 0.2 to 20 g / 10 min. I need that.
The melt flow rate (MFR) of the propylene-based polymer (X) is 0.2 to 20 g / 10 minutes. When the MFR is less than 0.2 g / 10 minutes, the fluidity is lowered and the rigidity is also lowered. . On the other hand, when the MFR exceeds 20 g / 10 min, the melt processability decreases. Moreover, within this range, it is preferably 0.5 to 15 g / 10 minutes, more preferably 0.7 to 10 g / 10 minutes, and particularly preferably 1 to 5 g / 10 minutes.
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 (X) adjusts the temperature and pressure, which are the polymerization conditions of the propylene polymer (X), and the amount of chain transfer agent such as hydrogen added during the polymerization. By controlling, adjustment can be easily performed.

(2-2) Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC:
As shown in the requirement (ii), the propylene polymer (X) according to the present invention is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), Mw / Mn (Q value) needs to be in the range of 3.5 to 10.5.
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 fluidity and workability becomes poor. Accordingly, the Q value needs to be 3.5 or more, preferably 4.0 or more. More preferably, it is 4.5 or more. 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) measured by GPC of the propylene-based polymer (X) can be changed by changing the temperature and pressure conditions of propylene polymerization, or the most general technique such as hydrogen Adjustment can be easily made by adding a chain transfer agent during the polymerization of propylene. Furthermore, when using 2 or more types of the metallocene complex to be used, it can control by changing the quantity ratio.

(2-3) Bias of molecular weight distribution obtained from GPC molecular weight distribution curve toward high molecular weight side:
As shown in the requirement (viii), the propylene polymer (X) according to the present invention has a common logarithm of molecular weight corresponding to the peak position as Tp and 50% higher than the peak height in the molecular weight distribution curve obtained by GPC. The common logarithm of the molecular weight at the position is L ₅₀ and H ₅₀ (L ₅₀ is a lower molecular weight side than Tp, H ₅₀ is a higher molecular weight side than Tp), and α and β are α = H ₅₀ −Tp and β = Tp, respectively. when defined as -L _50, alpha / beta is greater than 0.9 should be less than 2.0. Here, α / β is an index representing the deviation of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created by plotting the common logarithm of molecular weight (MW) on the horizontal axis and the relative differential mass of the molecule corresponding to the MW 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, it is desirable that α / β is greater than 0.9 and less than 2.0.

Usually, when uniform polymerization is carried out with a catalyst having a single active site, the molecular weight distribution has the most probable distribution shape. The most probable distribution α / β is calculated as 0.9.
Therefore, the molecular weight distribution of the propylene homopolymer, which is the propylene-based polymer (X) according to the present invention, further spreads to the higher molecular weight side than the molecular weight distribution of the polymer polymerized uniformly at a single active site. It means that
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, in the case of performing solid-state pressure forming, in the sheet forming stage, the lower the viscosity, the higher the gloss, so it is better that there are many components having a low viscosity. On the other hand, at the stage of container molding, if the portion is not strong, it will break, so 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.
Accordingly, it is desirable that the propylene-based polymer (X) according to the present invention has α / β larger than 0.9, preferably 1.0 or more, and more preferably 1.1 or more.

On the other hand, when α / β is 2.0 or more, the amount of the high molecular weight component is too large and the fluidity is deteriorated. 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.
Accordingly, the propylene-based polymer (X) according to the present invention desirably has an α / β value of less than 2.0, preferably less than 1.7, and more preferably less than 1.6.
In the molecular weight distribution curve, two or more peaks may appear. In that case, the maximum peak can be replaced with the peak of the present invention. Also, if the H ₅₀ appears two or more may be replaced with the molecular weight of the lowest molecular weight side. Similarly, when two or more L ₅₀ appear, the molecular weight on the lowest molecular weight side can be replaced.
The molecular weight distribution spread from the molecular weight distribution curve by GPC of the propylene-based polymer (X) was selected so that a high molecular weight polymer could be produced as one of the two types of metallocene complexes used. In addition, the adjustment can be easily performed by controlling the amount of hydrogen added during the polymerization. It can also be adjusted by changing the amount ratio of the two metallocene complexes used.

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

As described above, when the amount of the high molecular weight component is insufficient, the melt tension and the swell ratio are decreased, and the thermoformability is deteriorated. For example, when solid-phase pressure molding is performed, a fracture phenomenon occurs and a satisfactory molded body cannot be obtained. 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 (X) 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 extrusion sheet formability is deteriorated. In addition, since it is a component having a very high molecular weight, a gel is generated, resulting in a problem that the appearance of the molded product is impaired. Moreover, when the ratio of this component is too high, when deep drawing is performed at the time of thermoforming, a so-called melt ductility is deteriorated, in which the melt breaks.
Therefore, the propylene polymer (X) according to the present invention desirably has W (2 million or more) less than 10% by weight, preferably less than 6.0% by weight, more preferably 5.0%. Less than% by weight.

The ratio of the component having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC of the propylene-based polymer (X) is selected after a high molecular weight polymer can be produced as the metallocene complex to be used. Adjustment can be easily made by controlling the amount ratio of the metallocene complex to the metallocene complex, 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 the 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 generates 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.
The following numerical value is used for the viscosity formula: [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 −4, α = 0.7
PP: K = 1.03 × 10−4, α = 0.78

(2-5) Temperature rising elution fractionation with orthodichlorobenzene (ODCB) (TREF):
As shown in the requirement (iv), the propylene-based polymer (X) according to the present invention has a component that elutes at a temperature of 40 ° C. or lower in an elution curve obtained by temperature rising elution fractionation (TREF) measurement of 3.0. % By weight or less.
A component that elutes at a temperature of 40 ° C. or lower is a low crystalline component. If the amount of this component is large, the crystallinity of the entire product is lowered, and the mechanical strength such as the rigidity of the product is lowered.
Therefore, this amount should be 3.0% by weight or less, preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and most preferably 0.5% by weight or less. is there.
The temperature rising elution fractionation (TREF) of the propylene polymer (X) with orthodichlorobenzene (ODCB) can generally be 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 production method of the catalyst and the reaction conditions at the time of polymerization are not extremely high and the amount ratio of the organoaluminum compound to the metallocene complex is not excessively increased.

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

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

(2-6) Isotactic triad fraction (mm) measured by ¹³ C-NMR:
As shown in the requirement (v), the propylene polymer (X) according to the present invention has a stereoregularity in which the mm fraction of three propylene units 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 stereoregular ability of the catalyst components [A-1] and [A-2] used in the production method of the propylene polymer (X) described later. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is degraded. Therefore, in order to obtain a higher rigidity polymer, it is preferable that the side chain and the main chain have high stereoregularity. As the value, the main chain and the side chain are 95% or more in mm fraction. Especially preferably, it is 96% or more, More preferably, it is 97% or more.
The isotactic triad fraction (mm) measured by ¹³ C-NMR of the propylene polymer (X) can be easily adjusted by the selection of the metallocene complex described later, the polymerization temperature and the polymerization pressure.

The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg was completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.2 ppm at the center of the three peaks of deuterated 1,1,2,2-tetrachloroethane. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
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, (1975) 8 pp. 687 and Polymer, 30 vol. 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 slightly shifts depending on the molecular weight and copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structure.

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

  Moreover, the propylene polymer (X) 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).

(2-7) Strain hardening degree (λmax) in measurement of elongational viscosity:
The propylene polymer (X) according to the present invention needs to have a strain hardening degree (λmax) of 6.0 or more in the measurement of elongational viscosity, as shown in the requirement (vi).
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, the thickness uniformity of the deep-drawn molded body is improved when solid-phase pressure 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.
Furthermore, strain hardening is currently considered the most sensitive method for evaluating branching, and it is difficult to evaluate the branched structure directly by ¹³ C-NMR. The strain hardening degree was used as an index of branching.

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-based polymer (X) according to the present invention is, as described above, a skeleton carbon number of 500 (polypropylene molecular weight conversion: 11,000) or more, preferably a skeleton carbon number of 1000 (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. Therefore, the branch length of the propylene-based polymer (X) 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 degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene polymer (X) 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. It can be increased to 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 measuring instrument are disclosed in Polymer 42. Although there are methods described in (2001) 8663, examples of preferable measuring methods and measuring instruments include the following.

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

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

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (seconds) on the horizontal axis and elongational viscosity ηE (Pa · seconds) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain reaches 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity.
FIG. 4 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The 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.

(2-8) Memory effect (ME):
The propylene polymer (X) according to the present invention desirably has a memory effect (ME) satisfying the following formula (I-1) as shown in the requirement (vii).
(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 (X) according to the present invention preferably has a correlation between a memory effect (ME) that is an index that represents an abundance ratio of a high molecular weight component in a polymer and an MFR that is an index that represents an average molecular weight of the polymer. 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 (X) according to the present invention has a large ME in MFR match as compared with conventionally known polymers, 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 uneven thickness of the deep-drawn molded product obtained by solid-phase pressure molding is suppressed, and the propylene polymer (X) according to the present invention is excellent in thermoforming 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) of the propylene-based polymer (X) controls the selection and combination of the metallocene complexes (to be described later) used in the polymerization of the propylene-based polymer (X), the amount ratio, and the prepolymerization conditions. By doing so, adjustment can be performed.

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

(2-9) Melt tension and melt spreadability:
Since the propylene polymer (X) according to the present invention has a controlled branch structure (branch amount, branch length, branch distribution), the melt properties are remarkably improved. That is, it has excellent melt fluidity while having high melt tension. As an index of melt tension and melt fluidity, it can be expressed by a balance between melt tension (MT) and maximum winding speed (MaxDraw) measured by the following measurement method.

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

When the winding speed is gradually increased from 4.0 m / min (acceleration: 5.4 cm / s2), the winding speed immediately before the string-like material is cut is set as the maximum winding speed (MaxDraw). .
Here, a larger MT value means higher melt tension, and a larger MaxDraw means better fluidity and spreadability.
The propylene-based polymer (X) according to the present invention has improved melt tension by broadening the molecular weight distribution and introducing branching. Therefore, MT is 5 g or more, preferably 10 g or more, more preferably 15 g. That's it.

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 (X) according to the present invention can have a large MaxDraw while maintaining a high MT by controlling the branched component, and the balance between melt tension and melt spreadability is improved.
Accordingly, the propylene polymer (X) 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-based polymer (X) to reduce non-homogeneous components such as a gel. In order to obtain a homogeneous propylene-based polymer (X), diene or the like In the macromer polymerization method using no catalyst, adjustment can be performed by controlling the prepolymerization conditions of the catalyst used and the polymerization conditions such as hydrogen concentration and temperature.

As described above, the propylene-based polymer (X) 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, Japanese Patent Application Laid-Open No. 2007-154121 discloses propylene homopolymers having a branch number of 0.1 / 1000 skeleton carbon or more, but distortion in measurement of elongational viscosity. The degree of cure (λmax) is less than 6, and even when the degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) according to the present invention is 6.0 or more, the effect of improving the melt properties is effective. Not enough. 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 cutting 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, deterioration of mechanical properties and heat sealability occur.
However, the propylene-based polymer (X) according to the present invention is controlled by expanding the molecular weight distribution by broadening the molecular weight distribution and introducing a branch, 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.
As described above, since the propylene polymer (X) according to the present invention is a long-chain branched type, the physical properties and processability are controlled by controlling the melt ductility and the melt tension not found in the conventional propylene polymer. It has become an excellent balance.

(3) Propylene Polymer (X) Production Method About the method of producing the propylene polymer (X) according to the present invention, the balance between physical properties and processability is controlled by controlling the melt fluidity and melt tension. There is no particular limitation as long as it is a method for obtaining an excellent long-chain branched propylene-based polymer. For example, examples of a method for introducing a controlled branched component include a method using a plurality of complexes as described below. be able to.

That is, a method for producing the long-chain branched propylene-based polymer, wherein the following catalyst components (A), (B), and (C) are used as propylene polymerization catalysts: The manufacturing method of a 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.
(A) Catalyst component (A)
(I) Component [A-1]: Compound represented by general formula (a1)

[In General Formula (a1), each of R11 and R12 independently represents a heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms. R13 and R14 each independently represent an aryl group having 6 to 16 carbon atoms that may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, A heterocyclic group containing nitrogen, oxygen, or sulfur having 6 to 16 carbon atoms. X11 and Y11 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q11 is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom It represents a silylene group or a germylene group which may have ˜20 hydrocarbon groups. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R11 and R12 is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted group. It is a 2-furfuryl group, and 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}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-i [Denyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl) -2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1 '-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1, '-Dimethylsilylenebis {2- (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′-dimethylsilylene Bis {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-naphthyl) -indenyl}] haf , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4 -(1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilane Rylenebis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) { 2- (5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2 -Thienyl) -4-phenyl-indenyl}] hafnium, 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, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M21 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, 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.

(B) Catalyst component (B)
Next, the catalyst component (B) used for the polymerization of the propylene-based polymer (X) according to 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 size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (B).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product. 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. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In the present invention, a combination of the following acids and salts may be used as the treating agent. 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>:
Examples of the organic treatment agent used for organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. It is not limited to these.

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

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

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

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

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

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

(C) Catalyst component (C)
The catalyst component (C) used for the polymerization of the propylene polymer (X) according to the present invention is an organoaluminum compound. The organoaluminum compound used as the catalyst component (C) is suitably a compound represented by the general formula: (AlR11qZ3-q) p.
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, R11 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. R11 is preferably an alkyl group, and Z is a chlorine atom when it is halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. The amino group of is preferable.

  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, R11 is a trialkylaluminum having 1 to 8 carbon atoms.

(D) Formation of catalyst / 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 several 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. Particularly preferable ones for each component are as follows.
When the catalyst component (C) is used, before the catalyst component (A) and the catalyst component (B) are contacted, the catalyst component (A), or the catalyst component (B), or the catalyst component (A) and the catalyst Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of the catalyst components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of catalyst 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 catalyst component (B). The amount of the catalyst component (C) used relative to the catalyst component (B) is preferably in the range of 0.01 to 1000 mmol, particularly preferably 0.05 to 500 mmol, with respect to 1 g of the catalyst component (B). Therefore, the amount of the catalyst component (C) relative to the catalyst component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably in the range of 0.1 to 1 × 10 ⁴ , in terms of the molar ratio of the transition metal. preferable.

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 propylene polymer (X) 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-based polymer (X) 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 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 catalyst component (B). Moreover, a catalyst 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.

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

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.
The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

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

Moreover, you may perform the copolymerization which uses C2-C20 (except what is used as a monomer) alpha olefin as a comonomer other than a propylene monomer. 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 (X) according to the present invention in a good balance between melt physical properties and catalytic activity, it is preferable to use ethylene at 5 mol% or less. In order to obtain a polymer having particularly high rigidity, it is preferable to use ethylene so that ethylene contained in the polymer is 1 mol% or less, more preferably propylene homopolymerization.

(F) Consideration of polymerization mechanism It is considered that the formation of the macromer is caused by a special chain transfer reaction generally called β-methyl elimination, and in the present invention, the component [A-1] having a specific structure is compared. In a 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 a complex having a conventional structure It has been found to be large compared to
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 the component [A-1] having a specific structure, industrially effective bulk polymerization or gas phase polymerization, and practical pressure conditions (1.0 to 3.0 MPa) and temperature conditions (40 ° C. It was found that the production is possible under ˜80 ° C.).

Furthermore, surprisingly, by adding hydrogen, the chain transfer reaction by hydrogen is superior to the β-methyl elimination reaction in the conventional method, whereas the cause is unknown, but according to the present invention. The propylene-based polymer (X) production method is characterized by a small change in the balance between macromer formation and growth reaction even when hydrogen is added, and it has been found that the selectivity of the macromer remains almost unchanged even in the presence of hydrogen. . Moreover, hydrogen has an activity improving effect.
This is because, in the past, it has been necessary to carry out a multi-stage polymerization in which a macromer copolymerization is performed after a macromer production 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, the component [A-2] has a specific structure, so that it has a high ability to copolymerize macromers even though it does not have the ability to form a terminal vinyl structure. 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 is possible to produce a long-chain branched propylene polymer (X) having the following physical properties:
In the past, the branching efficiency was increased only under conditions for producing a polymer with low stereoregularity, but in the method of the present invention, a sufficiently high stereoregularity component was introduced into the side chain by a simple method. It became possible to do.

2. Propylene polymer (Y)
The propylene-based polymer (Y) constituting the propylene-based resin composition used for the polypropylene-based deep-drawn molded article of the present invention is either a propylene homopolymer or a copolymer of propylene and another α-olefin. A copolymer of propylene and an α-olefin, particularly a propylene / α-olefin random copolymer may be preferable.

  The propylene / α-olefin random copolymer preferably used is a random copolymer of propylene and an α-olefin mainly composed of a structural unit derived from propylene. The α-olefin used as a comonomer is preferably ethylene or an α-olefin having 4 to 18 carbon atoms. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1 etc. can be mentioned. Moreover, as an alpha olefin, 1 type or the combination of 2 or more types may be sufficient.

  Specific examples of the propylene / α-olefin random copolymer include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene / ethylene / 1- Examples include octene random copolymers and propylene / ethylene / 1-butene random copolymers.

The amount of the propylene unit in the propylene / α-olefin random copolymer is not particularly limited, but is preferably 88 to 99.5% by weight, and more preferably 91 to 99% by weight. If the propylene unit amount is significantly less than 88% by weight, the rigidity of the polypropylene-based deep-drawn molded product tends to be lowered, whereas if it is more than 99.5% by weight, HAZE may be lowered.
Here, the propylene unit and the α-olefin unit are values measured by a ¹³ C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

(1) Characteristics (i) to (iv) of the propylene polymer (Y)
The propylene polymer (Y) used in the present invention preferably has the following characteristics (i) to (iv). Hereinafter, each characteristic will be described.

Characteristic (i) MFR:
The melt flow rate (MFR) of the propylene polymer (Y) used in the present invention is 0.5 to 20 g / 10 min, preferably 0.7 to 10 g / 10 min, more preferably 1 to 5 g / 10 min. is there. When the MFR is less than 0.5 g / 10 min, the viscosity of the molten resin is high and the sheet formability is inferior. On the other hand, when the MFR exceeds 20 g / 10 min, the viscosity of the molten resin is low and the drawdown is large during sheet molding Therefore, it is not preferable.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 21.2 N in accordance with JIS K7210.
The melt flow rate (MFR) of the propylene polymer (Y) is the amount of hydrogen added to adjust the temperature and pressure, which are the polymerization conditions of the propylene polymer (Y), or to add a chain transfer agent such as hydrogen during the polymerization. Adjustment can be easily performed by controlling the above.

Characteristic (ii) Melting peak temperature (Tm):
The melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC) of the propylene-based polymer (Y) used in the present invention is preferably 120 to 165 ° C, and preferably 130 to 160 ° C. Is more preferable. When Tm is less than 120 ° C., the rigidity of the propylene-based deep-drawn molded product is unfavorable, and when Tm exceeds 165 ° C., HAZE of the propylene-based deep-drawn molded product may decrease. It is not preferable.
In order to adjust Tm, it can adjust easily by controlling the quantity of the alpha olefin supplied to a polymerization reaction system.
Here, the specific measurement of Tm is performed using a differential scanning calorimeter (DSC), taking a sample amount of 5 mg, holding at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of temperature decrease of 10 ° C./min. Further, the peak position of the curve drawn when the film is melted at a temperature rising rate of 10 ° C./min is defined as a melting peak temperature Tm (° C.).

Characteristic (iii) Molecular weight distribution (Mw / Mn):
The molecular weight distribution (Q value: Mw / Mn) measured by the gel permeation (GPC) method of the propylene-based polymer (Y) used in the present invention is preferably 1.5 to 4.5, More preferably, it is less than 1.8-4. When the Mw / Mn is less than 1.5, it is difficult to obtain with the current polymerization technique. On the other hand, when the Q value exceeds 4.5, the HAZE of the polypropylene-based deep-drawn molded product is lowered, which is not preferable.
The molecular weight distribution of the propylene polymer (Y) can be adjusted by selecting a catalyst to be used and a polymerization method. For example, when a metallocene catalyst is used, polymerization is performed using a catalyst system in which two or more metallocene catalyst components are used in combination or a catalyst system in which two or more metallocene complexes are used in combination, or two or more stages of multistage polymerization are performed during polymerization. It can be controlled by doing. On the contrary, in order to narrowly adjust the molecular weight distribution, it can be adjusted by polymerizing a propylene polymer and then melt-kneading it using an organic peroxide.
Here, molecular weight distribution is calculated | required by the ratio (Q value: Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn), and a gel permeation chromatography similarly to the propylene polymer (X) mentioned above. Obtained by measurement by a graphic (GPC) method.

Characteristic (iv) T ₈₀ -T ₂₀ (elution amount difference temperature by TREF):
Extraction temperature (T ₂₀ ) and 80 wt% are extracted in an elution curve obtained by temperature rising elution fractionation (temperature rise elution fractionation: TREF) of the propylene-based polymer (Y) used in the present invention. temperature difference _{(T 80) (T 80 -T} 20) is preferably not 10 ° C. or less. If it exceeds 10 ° C., the composition distribution in the polymer becomes non-uniform, and it is difficult to make the foam cell diameter uniform, which is not preferable.
T ₈₀ -T ₂₀ (elution amount difference temperature by TREF) of the propylene-based polymer (Y) can be adjusted by using a catalyst using a metallocene complex and controlling the catalyst production conditions. Measurement conditions are the same as those of the propylene polymer (X) described above.

(2) Polymerization method of propylene polymer (Y) The propylene polymer (Y) used in the present invention is preferably polymerized using a metallocene catalyst. Use of polypropylene polymerized with a catalyst other than a metallocene catalyst is not preferable because the molecular weight distribution is wide, the composition distribution is not uniform, and the haze (HAZE) of the deep-drawn molded article is deteriorated.

  The metallocene catalyst used for the polymerization of the propylene-based polymer (Y) used in the present invention is (i) a transition metal compound belonging to Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton. (Ii) A catalyst comprising a promoter capable of reacting with a metallocene compound to be activated to a stable ionic state and, if necessary, (iii) an organoaluminum compound. Any known catalyst can be used. The metallocene compound is preferably a bridged metallocene compound capable of stereoregular polymerization of propylene, and more preferably a bridged metallocene compound capable of isoregular polymerization of propylene. Each component will be described.

  Examples of (i) metallocene compounds include JP-A-60-35007, JP-A-63-130314, JP-A-63-295607, JP-A-1-275609, JP-A-2-41303, and JP-A-2-41303. JP-A-2-131488, JP-A-2-76887, JP-A-3-163888, JP-A-4-30087, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, and JP-A-8-85708.

More specifically, methylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl) -4H-azulenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (2- Methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5 , , 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-phenylindenyl)] zirconium Dichloride, dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, dimethylsilylene (fluorenyl) t-butylamidozirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4, ( 1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenyl-4H) -Azulenyl) ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] Zirconium dichloride, diphenylsilylene bis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4- (3-fluorobiphenylyl) ) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-) 4-phenylindenyl)] zirconium Zirconium compounds such as chloride can be exemplified. In the above, compounds in which zirconium is replaced with titanium or hafnium can be used in the same manner. In some cases, a mixture of a zirconium compound and a hafnium compound can be used. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl, isobutyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Among these, a metallocene compound in which an indenyl group or an azulenyl group is crosslinked with silicon or a germyl group is preferable.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous compound. Specifically, ion-exchange layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B Examples include inorganic compounds such as ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , organic compounds composed of porous polyolefin, styrene / divinylbenzene copolymer, olefin / acrylic acid copolymer, and the like, or a mixture thereof. It is done.

  (Ii) As a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound, an organoaluminum oxy compound (for example, an aluminoxane compound), an ion-exchange layered silicate, a Lewis acid, a boron-containing compound, an ionic compound And fluorine-containing organic compounds.

  (Iii) Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and organoaluminum alkoxide. Can be mentioned.

Examples of the polymerization method include a slurry method using an inert solvent in the presence of the catalyst, a solution method, a gas phase method substantially using no solvent, or a bulk polymerization method using a polymerization monomer as a solvent. . As a method for obtaining a propylene-based polymer (Y) used in the present invention, particularly a propylene / α-olefin random copolymer, for example, the polymerization temperature and the comonomer amount are adjusted to appropriately control the molecular weight and crystallinity distribution. Thus, a desired polymer can be obtained.
Such a propylene / α-olefin random copolymer may be appropriately selected from those commercially available as metallocene polypropylene. Examples of commercially available products include “Wintech” manufactured by Nippon Polypro.

3. Blending ratio of propylene polymer (X) and propylene polymer (Y) In the polymer mixture used for the polypropylene-based deep-drawn molded article of the present invention, the propylene polymer (X) and the propylene polymer (Y ) In a proportion of 3 to 100% by weight of the propylene polymer (X), 0 to 97% by weight of the propylene polymer (Y), and preferably 5 to 5% of the propylene polymer (X). 90% by weight and 10 to 95% by weight of the propylene polymer (Y). When the blending amount of the propylene-based polymer (X) is less than 3% by weight, the thickness uniformity of the resulting propylene-based deep-drawn molded product is deteriorated.

4). Crystal nucleating agent In the present invention, in order to improve rigidity and transparency, it is preferable that a crystal nucleating agent is blended in the propylene-based resin composition.
The blending amount of the crystal nucleating agent is 100 parts by weight of the polymer mixture, or the polymer mixture contains a polymer other than the propylene polymer (X) and the propylene polymer (Y). Is in the range of 0.01 to 1 part by weight, preferably 0.02 to 0.8 part by weight, more preferably 0.04 to 0.5 part by weight, based on 100 parts by weight of the polymer mixture. Part. If the blending amount of the crystal nucleating agent is significantly out of this range, the effect of improving the rigidity may not be obtained sufficiently, which is not preferable.

Examples of the crystal nucleating agent preferably used in the present invention include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, Pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-tert-butylphenyl) sodium phosphate, 2,2′-methylenebis (4,6-di-t) phosphate -Butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphosphocin-6-oxide) A complex of an aluminum hydroxide salt and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, a sodium salt of rosin, and the like are preferable.
A commercially available crystal nucleating agent can be used. For example, trade names Adeka Stub NA11 and NA21 manufactured by Adeka, Gelall MD manufactured by Shin Nippon Chemical Co., Ltd., Milad NX3988 and Mirad NX8000 manufactured by Milliken, and the like can be mentioned.

5. Other compounding agents In addition to the propylene polymer (X), the propylene polymer (Y) and the crystal nucleating agent, the propylene resin composition used for the polypropylene deep-drawn molded article of the present invention is usually a polyolefin. Other known polymers used in the field, such as antioxidants, neutralizers, light stabilizers, UV absorbers, inorganic fillers, antiblocking agents, lubricants, antistatic agents, metal deactivators, and other polypropylenes Various additives such as polymers that can be used can be blended within a range that does not impair the object of the present invention.

Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants, and examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, nickel complex compounds, benzotriazoles, and benzophenones.
Examples of the other polymer include propylene alone or a copolymer of propylene and another α-olefin, polymers such as low density polyethylene and high density polyethylene, and various thermoplastic elastomers.

II. Method for Preparing Propylene Resin Composition As a method for preparing the propylene resin composition used in the present invention, the propylene polymer (X) in the form of powder or pellets, propylene polymer, crystal nucleating agent and A method of mixing other compounding agents to be used as necessary with a dry blend, a Henschel mixer or the like can be mentioned.
Further, depending on the situation, only the crystal nucleating agent may be separately fed during the production of the polypropylene thermoformed sheet.

III. Polypropylene-based sheet The sheet used in the present invention is passed through a known monoaxial or biaxial screw extruder and extruded from a coat solder die into a sheet shape. It can be obtained by cooling and solidifying by pressing an air knife, an air chamber, a hard rubber roll, a steel belt, and a metal roll on the surface of the metal roll where oil is circulating. It is also possible to cool and solidify both sides of the sheet with a steel belt.
Among such sheet cooling methods, a method using metal rolls and / or steel belts on both sides of the sheet is the most preferable method because a sheet surface with less surface irregularities, that is, a sheet having excellent transparency can be obtained. .
The sheet used in the present invention can be used as a multilayer sheet in addition to a single layer. A multilayer sheet is an extruder equipped with a plurality of dies, and is a multilayer sheet in which a gas barrier resin layer, an adhesive resin layer, a recycled resin layer, a candle resin layer, etc. are stacked using a feed block or a multi-manifold. I can do it.

The thickness of the sheet used in the present invention is preferably 0.3 to 4 mm, more preferably 0.5 to 3.5 mm, and particularly preferably 0.8 to 3 mm.
When the thickness is significantly less than 0.3 mm, the rigidity of the blown-out molded article is impaired, and when the thickness is significantly greater than 3 mm, sheet molding may be difficult.
The sheet used in the present invention preferably has a tensile modulus of 1000 Mpa or more, more preferably 1200 Mpa or more, and particularly preferably 1400 Mpa or more.
When the tensile elastic modulus is 1000 Mpa or more, the deep-drawn molded body obtained by solid-phase pressure forming has high rigidity, so that it can be used very suitably for applications such as industrial packaging containers and packaging materials. it can.
A tensile elasticity modulus means the average value of the value of MD obtained by the postscript evaluation method, and the value of TD.
Further, the sheet used in the present invention preferably has a haze (HAZE) of 55% or less, more preferably 45% or less, and particularly preferably 35% or less.
When the haze of the sheet is 55% or less, the transparency of the deep-drawn molded product obtained by solid-state pressure forming of the sheet can be enhanced.

Further, the sheet used in the present invention preferably has a Gloss value (gross value) of 100% or more, more preferably 110% or more, and particularly preferably 120% or more.
When the gloss value of the sheet is 100% or more, the gloss of the deep-drawn molded product obtained by solid-state pressure forming of the sheet can be increased.
The sheet used in the present invention may be any sheet surface treatment such as corona discharge treatment, flame treatment, plasma treatment, etc., or a lubricant or antifogging agent applied.

III. Deep-drawn molded body The deep-drawn molded body of the present invention can be obtained by subjecting a sheet to solid-phase pressure molding at a temperature below the melting point. Examples of the heating method in such thermoforming include indirect heating, hot plate heating, and hot roll heating. When thermoforming is performed at a temperature exceeding the melting point of the sheet, the transparency, gloss, and thickness uniformity of the resulting deep-drawn molded article deteriorate.
The deep drawing in the present invention refers to one having a drawing ratio of 1.0 or more, which is a ratio of the depth of the formed body to the (maximum) width, regardless of whether the shape of the formed body is a square shape or a round shape.
The deep-drawn molded article of the present invention has a drawing ratio of 1.0 or more, preferably 1.2 or more, more preferably 1.5 or more.
Further, the deep-drawn molded article of the present invention has a haze (HAZE) of 5% or less, preferably 3% or less, and particularly preferably 1.5% or less.
Further, the polypropylene-based deep-drawn molded article of the present invention has a gloss value of 120% or more, preferably 130% or less, and particularly preferably 150% or more.
When the haze (HAZE) is 5% or less and the gloss value is 120% or more, the deep-drawn molded article has high transparency and gloss, so that it can be used for pharmaceuticals, industrial products, foods and daily necessities. It can be used very suitably for applications such as packaging containers.

IV. Use of deep-drawn molded article The deep-drawn molded article of the present invention is excellent in transparency and gloss, and can be used for containers in various fields such as food containers, detergent containers, and medical containers. It can be widely used in the beverage food field where the contents can be confirmed.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, various physical properties of the deep-drawn molded product or its constituent components were measured and evaluated according to the following evaluation methods, and the following resins were used as the used resins (used materials). .

1. Evaluation method (1) Melt flow rate (MFR) [unit: g / 10 min]:
The propylene-based resin conforms to JIS K7210: 1999 “Method of plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test”, condition M (230 ° C., 2.16 kg load). Measured in conformity.
(2) Melting point (Tm) and crystallization temperature (Tc):
Using a DSC6200 manufactured by Seiko Instruments Inc., the sample piece made into a sheet is 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 crystallized, 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.).
(3) Molecular weight and molecular weight distribution (Mw, Mn, Q value):
It was measured by the method described in the present specification by gel permeation chromatography (GPC).

(4) Temperature rising elution fractionation (TREF):
The TREF measurement method is as described in the present specification using the following apparatus.
(I) TREF part TREF column: 4.3 mmφ × 150 mm stainless steel column Column filler: 100 μm surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (ii) Sample injection part Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Iii) Detection unit Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5mm Window shape 2φ x 4mm oval Synthetic sapphire window Measurement temperature: 140 ° C
(Iv) Pump unit Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. (v) Measurement conditions Solvent: o-dichlorobenzene (including 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(5) 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). When this value is large, the swell is large and the product appearance is improved when cooled and solidified by a metal roll and / or metal belt in sheet forming. (As injection molding is not relevant, please give another reason.)
(6) mm fraction:
The measurement was carried out by the method described in the present specification using GSX-400 and FT-NMR manufactured by JEOL. The unit is%.
(7) Measurement of ethylene content:
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.
(8) Elongation viscosity:
It was measured by the method described in the present specification.
(9) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.

(10) Sheet physical properties:
The tensile modulus, HAZE, and gloss value of the sheet obtained in each of the examples and comparative examples were measured.
Here, the tensile elastic modulus was measured according to JIS K7127, HAZE was measured according to JIS K7136, and the gloss value was measured according to JIS K7105.

(11) Haze value of deep drawn compact
Standard number: JIS K7136 (ISO 14782) "Plastics-Determination of haze of transparent material" and JIS K7361-1 (ISO 13468-1) "Plastic-Test method of total light transmittance of transparent material-Part 1: Single beam method compliant Measuring instrument: Haze meter NDH2000 (Nippon Denshoku Industries Co., Ltd.)
Test piece thickness: 200 μm
Preparation of test piece: Cut out from molded body to 50 × 50 mm Condition adjustment: After molding, left in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% Number of test pieces: 3
Evaluation item: Haze

(12) Gloss value of deep-drawn molded article The gloss of the test piece was evaluated under the following conditions.
Standard number: JIS K7105 "Testing method for optical properties of plastics"
Measuring machine: Digital variable angle gloss meter UGV-5K manufactured by Suga Test Instruments
Test piece thickness: 200 μm
Preparation method of test piece: Cut out from molded body to 50 × 50 mm Condition adjustment: After molding, left in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% Number of test pieces: 3
Evaluation item: 60 degree specular gloss (13) Uneven thickness of deep-drawn molded article:
At the center of the body of the deep-drawn molded body (the height of the molded body / 2 cm), the thickness in the circumferential direction was measured with a Mitutoyo micrometer, and the difference between the maximum value and the minimum value was determined. It means that the smaller the numerical value, the more uniform the thickness of the cylindrical bottle, the smaller the uneven thickness, and the better the product. If the difference between the maximum value and the minimum value is 0.02 or less, the wall thickness is uniform.

2. Materials used (1) Propylene polymer (X)
The polymers (PP-1) to (PP-4) produced in the following Production Examples 1 to 4 and a commercially available polypropylene resin (PF814) were used.

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

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

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

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

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

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

The identification value by the proton nuclear magnetic resonance method (1H-NMR) about the obtained racemic body is described below.
[1H-NMR (CDCl3) identification result]:
Racemate: δ 0.95 (s, 6H), δ 1.18 (s, 18H), δ 2.09 (s, 6H), δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ6. 75 (dd, 2H), δ 7.09 (d, 2H), δ 7.34 (s, 2H), δ 7.33 (d, 2H), δ 7.35 (d, 4H), δ 7.87 (d, 4H ).

[Synthesis Example 2 of Catalyst Component (A)]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: (synthesis of [A-2] (complex 2)) :
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.

(2) [Catalyst Synthesis Example 1]
(2-1) 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, and the entire amount of the above solid on the cake was added, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(2-2) Catalyst preparation and prepolymerization:
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 until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-t-butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (solution 1), and further, the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (45 μmol) prepared in Example 2 was dissolved in toluene (12 mL) (Solution 2 ).

After adding triisobutylaluminum (0.6 mmol: 0.83 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, add the above solution 1, and then add the above solution 2 after 5 minutes. And stirred at room temperature for 1 hour.
Thereafter, 356 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Thereafter, the propylene feed was stopped, the temperature was raised to 50 ° C., and residual polymerization was performed until the pressure in the autoclave reached 0.05 MPa. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.3 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 2 hours to obtain 27.5 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.75 (preliminary polymerization catalyst 1).

(3) [Polymerization]
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 5 liters of hydrogen (as a standard volume) and 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was raised to 75 ° C. Next, 4.0 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 75 ° C. After 3 hours, 100 ml of ethanol was injected under pressure, unreacted propylene was purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
The obtained polymer was dried for 1 hour under a nitrogen stream at 90 ° C. to obtain 14.5 kg of a polymer (PP-1). The catalytic activity was 3630 (g-PP / g-cat).
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.

[Production Example 2 (PP-2)]
The same procedure as in Production Example 1 was conducted except that 12.5 liters of hydrogen were added and 3.0 g of the prepolymerized catalyst 1 to be used (by weight excluding the prepolymerized polymer) was used. 14.3 kg of polymer (PP-2) was obtained. The catalytic activity was 4770 (g-PP / g-cat).

[Production Example 3 (PP-3)]
(1) [Catalyst synthesis example 2]
In (1-2) catalyst preparation and prepolymerization in Catalyst Synthesis Example 1, rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t- Butylphenyl) -indenyl}] hafnium (75 μmol) is dissolved in toluene (21 mL) to form solution 1, and rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl)- 4-hydroazurenyl}] hafnium (75 μmol) was dissolved in toluene (21 mL) and used as Solution 2, and the same experiment as in Catalyst Synthesis Example 1 was performed.
As a result, 30.9 g of a dry prepolymerization catalyst (preliminary polymerization catalyst 2) was obtained. The prepolymerization ratio was 2.09 (preliminary polymerization catalyst 2).

(2) [Polymerization]
Example 1 Polymerization Example 1 except that 7.5 L (as a standard state volume) of hydrogen was introduced and 2.0 g of the prepolymerized catalyst 2 synthesized above was used instead of the prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer. The same polymerization was carried out to obtain 11.4 kg of a polymer (PP-3). The catalytic activity was 5700 (g-PP / g-cat).

[Production Example 4 (PP-4)]
[Synthesis Example 3 of Catalyst Component (A)]:
(1) Synthesis of dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium:
In accordance with the method described in Example 1 of JP-A-8-208733, rac-dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium was synthesized.

(2) [Catalyst synthesis example 3]:
(2-1) Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1500 g) was added to 2260 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 480 minutes. The reaction slurry was cooled to room temperature in 1 hour and washed to pH 3 with distilled water. The resulting 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 dried at 215 ° C. under a nitrogen stream under a rotary kiln condition for 295 g of chemically treated smectite. Got.
The composition of the chemically treated smectite is Al: 2.72% by weight, Si: 43.48% by weight, Mg: 0.36% by weight, Fe: 0.61% by weight, and Al / Si = 0.065 [ mol / mol].

(2-2) Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above is added, and heptane (114 mL) is added to form a slurry, to which triethylaluminum (50 mmol: 81 mL of a heptane solution with a concentration of 71 mg / mL) is added. In addition, after stirring for 1 hour, the mixture was washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 200 mL.
In another flask (volume 200 mL), rac-dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium (0.3 mmol) was added to heptane (85 mL). Then, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added and reacted by stirring at room temperature for 60 minutes. This solution was added to the 1 L flask containing the chemically treated smectite and stirred for 60 minutes at room temperature. Thereafter, 214 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After setting the internal temperature of the autoclave to 40 ° C., propylene was fed at a rate of 20 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 2 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. The supernatant of the resulting catalyst slurry was removed by decantation, and triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the remaining portion, followed by stirring for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 47.6 g (preliminary polymerization catalyst 3) of a dry preliminary polymerization catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.38.

(3-3) Propylene polymerization:
Polymerization Example 1 except that 20 g of the prepolymerized catalyst 3 synthesized above was used instead of the prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer and the polymerization temperature was set to 70 ° C. for 3 hours without adding hydrogen. The same polymerization was carried out to obtain 6.9 kg of a polymer (PP-45). The catalytic activity was 345 (g-PP / g-cat). In particular, since this polymer has low catalytic activity, the amount of catalyst residue in the polymer is large, and there is a concern that the hue deteriorates during molding.

(2) Propylene polymer (Y)
WEG7T:
Propylene / ethylene random copolymer (using metallocene catalyst, ethylene 1.1 wt%, propylene 98.9 wt%, MFR = 1.4 g / 10 min, melting point 153 ° C.) manufactured by Nippon Polypro Co., Ltd.

(3) Other PF814 (electron beam irradiated product):
A high melt tension polypropylene (MFR = 2.5 g / 10 min, melting temperature 159.4 ° C.) manufactured by Basel Co., which is a commercially available polypropylene resin was used.

Crystal nucleating agent:
Product name ADK STAB NA21 manufactured by Adeka Co., Ltd .: Bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho A complex of (syn-6-oxide) aluminum hydroxide salt and an organic compound was used.

[Example 1]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-], which is a phenolic antioxidant, with respect to 100 parts by weight of the polymer (PP-1) produced in Production Example 1. Hydroxyphenyl) propionate] methane (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite, a phosphite antioxidant (Trade name: IRGAFOS 168, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts by weight, and calcium stearate as a neutralizing agent (trade name: calcium stearate, manufactured by Nippon Oil & Fats Co., Ltd.) 0.05 parts by weight , And 0.2 part by weight of “Adeka Stub NA21” which is a crystal nucleating agent, and a high-speed stirring mixer (Henschel mixer, trade name) Were mixed at room temperature for 3 minutes, and then melt-kneaded with an extruder to obtain pellets.

The above-mentioned pellets are put into an extruder having a screw diameter of 65 mm, a sheet cast by heat melting and plasticizing at a resin temperature of 230 ° C. and extruded from a T-shaped die is a mirror-finished metal cast roll whose surface temperature is controlled at 60 ° C. The sheet was continuously taken out at a speed of 1 m / min while being cooled and solidified in order to obtain a sheet having a width of 500 mm and a thickness of 1.6 mm.
Various evaluations described above were performed on this sheet. The results are shown in Table 1.
Next, this sheet was deep drawn by using a solid pressure air forming machine RDM50K (manufactured by Erich Co.) set to the deep drawing temperature shown in Table 2 and having a diameter of 95 mmφ and a depth / portion of 1.3 times. The body was molded.
The above-described various evaluations were performed on this deep-drawn molded body. The results are shown in Table 1.

[Example 2]
It implemented similarly to Example 1 except having used the polymer (PP-2) instead of the polymer (PP-1). The evaluation results are shown in Table 1.

[Example 3]
It implemented similarly to Example 1 except having used the polymer (PP-3) instead of the polymer (PP-1). The evaluation results are shown in Table 1.

[Example 4]
Instead of the propylene-based resin (PP-1), a polymer mixture obtained by blending 70% by weight of the propylene-based resin (PP-1) and 30% by weight of the propylene-based resin (Y: WEG7T) was used. The same operation as in Example 1 was performed. The evaluation results are shown in Table 1.

[Example 5]
Example except that a polymer mixture obtained by blending 20% by weight of polymer (PP-1) and 80% by weight of propylene resin (Y: WEG7T) was used instead of polymer (PP-1). 1 was carried out. The evaluation results are shown in Table 1.

[Comparative Example 1]
It implemented similarly to Example 1 except having used the propylene-type resin (PP-4) different from the propylene-type polymer (X) specified in this invention instead of the polymer (PP-1). The evaluation results are shown in Table 2.

[Comparative Example 2]
It implemented similarly to Example 1 using the electron beam irradiation bridge | crosslinking type propylene resin (PF814) different from the propylene polymer (X) specified in this invention instead of the polymer (PP-1). The evaluation results are shown in Table 2.

[Comparative Example 3]
It implemented similarly to Example 1 except having used the propylene polymer (Y: WEG7T) different from the propylene-type polymer (X) specified in this invention instead of the polymer (PP-1). The evaluation results are shown in Table 2.

  As is apparent from Tables 1 and 2 above, in Examples 1 to 5 that satisfy all the configurations of the present invention, a propylene-based deep-drawn molded article with less unevenness and excellent transparency and gloss was obtained. On the other hand, in Comparative Examples 1 to 3 that do not satisfy the configuration of the present invention, the obtained propylene-based deep-drawn molded article had a small HAZE value but a large uneven thickness, and a satisfactory molded article could not be obtained.

  Since the deep-drawn container of the present invention is excellent in moldability, rigidity, transparency and gloss, it can be used for containers in various fields such as food containers, detergent containers, and medical containers. It can be widely used in the field of beverages and foods where it can be confirmed. Therefore, the industrial applicability is very large.

Claims (7)

Propylene resin composition comprising a polymer mixture of 3 to 100% by weight of propylene polymer (X) satisfying the following requirements (i) to (vi) and 0 to 97% by weight of propylene polymer (Y) The sheet obtained from the above is obtained by solid-phase pressure molding at a temperature below the melting point, and the haze value is 5% or less and the gloss value is 120% or more, the wall thickness is uniform, A deep-drawn molded article having a depth / caliber of 1 or more times.
Requirement (i): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
Requirement (ii): The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
Requirement (iii): In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
Requirement (iv): In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
Requirement (v): The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
Requirement (vi): The strain hardening degree (λmax) in the measurement of elongational viscosity is 6.0 or more.   The polypropylene-based deep-drawn molded article according to claim 1, wherein the propylene-based resin composition contains 0.01 to 1 part by weight of a crystal nucleating agent with respect to 100 parts by weight of the polymer mixture.   The crystal nucleating agent is at least one selected from an aromatic carboxylic acid metal salt, an aromatic phosphate metal salt, a sorbitol derivative, an amide nucleating agent, and a metal salt of rosin. The polypropylene-based deep-drawn molded article as described. The polypropylene-based deep-drawn molded article according to any one of claims 1 to 3, wherein the propylene-based polymer (X) further satisfies the following requirement (vii).
Requirement (vii): ME (memory effect) satisfies the following relational expression.
(ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ] The polypropylene-based deep-drawn molded article according to any one of claims 1 to 4, wherein the propylene-based polymer (X) further satisfies the following requirement (viii).
Requirement (viii): In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where the peak height is 50% is L50 and H50 (L50 is from Tp When low molecular weight side, H50 is higher molecular weight side than Tp, and α and β are defined as α = H50−Tp and β = Tp−L50 respectively, α / β is greater than 0.9 and less than 2.0 is there. The propylene polymer (Y) is polymerized using a metallocene catalyst and satisfies the following characteristics (i) to (iv): The polypropylene-based deep-drawn molded article as described.
Characteristic (i): MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g / 10 min.
Characteristic (ii): Melting peak temperature (Tm) measured by DSC method is 120-165 ° C.
Characteristic (iii): Molecular weight distribution (Q value: Mw / Mn) measured by GPC method is 1.5 to 4.5.
Characteristic (iv): In an elution curve obtained by temperature rising elution fractionation (TREF), a difference (T80-T20) between a temperature (T20) extracted at 20% by weight and a temperature (T80) extracted at 80% by weight is 10 ° C. It is as follows.   The said polymer mixture consists of propylene polymer (X) 5 to 90 weight% and propylene polymer (Y) 10 to 95 weight%, The any one of Claims 1-6 characterized by the above-mentioned. The polypropylene-based deep-drawn molded article described in 1.

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