JP2017101229A - Biaxially stretched polypropylene sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biaxially stretched polypropylene sheet that is resistant to uneven stretching when stretching a sheet, and has excellent uniform stretchability, and a heat molding thereof.SOLUTION: The present invention provides a biaxially stretched polypropylene sheet that is obtained by biaxially stretching an extrusion sheet comprising a polypropylene resin composition obtained by mixing 100-5 wt.% of a propylene polymer (A) satisfying specific (i)-(vi) requirements, 0-95 wt.% of a propylene polymer (B), and a molding thereof.SELECTED DRAWING: None

Description

  The present invention relates to a biaxially stretched polypropylene sheet using a propylene polymer and a molded body.

  Conventionally, packaging products using thermoplastic resins such as polystyrene, polyethylene terephthalate, and polypropylene have been manufactured. Among thermoplastic resins, the propylene-based resin composition is excellent in heat resistance, rigidity, impact resistance, or hygiene, and thus is suitably used as a packaging for foods, etc., and particularly has high heat resistance. The range of use has been expanded to products that require a range up (heating) in a microwave oven, products that require high-temperature filling, and the like.

However, the propylene-based polymer has a disadvantage that its transparency is remarkably inferior particularly to polystyrene and polyethylene terephthalate because of its high crystallinity.
As a method for improving the transparency of the propylene-based polymer, for example, a method of improving the transparency by reducing the crystallinity by copolymerizing propylene and an α-olefin is used. In the method of improving transparency by copolymerization of propylene and α-olefin, transparency increases as the amount of α-olefin increases. However, the transparency improvement effect is naturally limited.

  Therefore, a method for improving transparency by adding and blending a propylene polymer with a nucleating agent such as dibenzylidene sorbitol, organic carboxylic acid, metal salt of organic carboxylic acid, metal salt of organic phosphate, etc. is generally used. . In particular, dibenzylidene sorbitol nucleating agents are most effective, and are widely used as packaging products for foods, daily necessities and the like (see Patent Document 1).

JP-A-4-339847

  On the other hand, after extruding a thermoplastic resin into a sheet shape, the sheet is reheated to obtain the desired product. Thermoforming methods such as vacuum forming, vacuum pressure forming, and solid pressure forming are easy to mold and productive. Since it is high, it is suitable for mass production and it is easy to obtain multi-layered products.

However, since polypropylene is a crystalline resin, compared to polystyrene and polyethylene terephthalate, in the case of thermoforming methods such as vacuum forming using an extruded sheet, vacuum pressure forming, etc., to reheat the sheet to make a product, It is difficult to obtain transparency, and it is difficult to mold a product that is valuable as a product.
Thus, there is a demand for a packaged product of a thermoformed article that has both transparency and rigidity using a polypropylene sheet having excellent heat resistance.

  An object of the present invention is to provide a biaxially stretched polypropylene sheet having uniform stretchability at low magnification stretching, and a molded body obtained by thermoforming this.

The present inventor has intensively studied to solve the above problems. As is well known, the polypropylene sheet is improved in physical properties such as rigidity and transparency by biaxial stretching.
In general, polypropylene, which is a crystalline resin, has a yield point. When low magnification stretching is performed, necking occurs and stretching unevenness (thickness unevenness) occurs. The draw ratio of the sequential biaxially stretched polypropylene known as OPP is usually carried out at a high magnification of about length × width = 5 × 10 times, but the desired stretched sheet (thickness 0.1-1 mm) ) Cannot be obtained because the thickness of the raw material becomes a problem.

  As a result of investigating a polypropylene resin in which stretching unevenness hardly occurs in low-stretch stretching, the present inventor comprises a biaxially stretched sheet using a specific propylene polymer and a resin composition containing the propylene polymer. It has been found that the biaxially stretched sheet is less likely to cause thickness unevenness in low magnification stretching and is excellent in uniform stretchability, and has completed the present invention.

That is, in the first invention of the present invention, the propylene-based polymer (A) characterized by satisfying the requirements defined in the following (i) to (vi) has a melting point measured by DSC of 100 to 5% by weight. A biaxially stretched polypropylene sheet obtained by biaxially stretching an extruded sheet made of a polypropylene resin composition containing 0 to 95% by weight of a propylene polymer (B) at 150 to 170 ° C is provided. .
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 g / 10 min or more and 20 g / 10 min or less.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
(Iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.

According to the second invention of the present invention, in the first invention, the propylene polymer (A) further satisfies the following requirements (vii) and (viii): A sheet is provided.
(Vii) (MT230 ° C.) ≧ 5 g
[In the formula, MT230 ° C. is measured using a melt tension tester, capillary: diameter 2.1 mm, cylinder diameter: 9.6 mm, cylinder extrusion speed: 10 mm / min, winding speed: 4.0 m / min, temperature: 230 It represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [where, MaxDraw (maximum winding speed) is the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. Represent. ]

According to the third invention of the present invention, in the first or second invention, the propylene polymer (A) further satisfies the following requirement (ix): Provided.
(Ix) (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. ]
Furthermore, according to the fourth invention of the present invention, in any one of the first to third inventions, the propylene-based polymer (A) further satisfies the following requirement (x): A polypropylene sheet is provided.
(X) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0.

  According to the fifth invention of the present invention, the stretched sheet of any one of the first to fourth inventions is stretched 1.5 times or more in each of MD and TD, and is 3 to 30 times in terms of surface magnification. A biaxially stretched polypropylene sheet obtained by stretching is provided.

［但し、式中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、炭素数が２〜２０のアルケニル基、炭素数が１〜２０のアルコキシ基、カルボニル基、ハロゲン基またはフェニル基であり、Ｒ６は、水素原子または炭素数が１〜２０のアルキル基である。 According to a sixth invention of the present invention, in any one of the first to fifth inventions, the nucleation represented by the following general formula (1) with respect to 100 parts by mass of the polypropylene resin composition A biaxially stretched polypropylene sheet characterized by containing 0.1 to 1 part by mass of an agent is provided.

[In the formula, n is an integer of 0 to 2, and R1 to R5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, a carbonyl group, a halogen group or a phenyl group, and R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

  Moreover, according to the 7th invention of this invention, the biaxially stretched polypropylene sheet of any one of the 1st-6th invention whose sheet thickness after extending | stretching is 0.1 mm-1 mm is provided.

  Moreover, according to the 8th invention of this invention, the biaxially-stretched polypropylene sheet of any one of the 1st-7th invention in which the standard deviation of the sheet | seat thickness after extending | stretching becomes 50 or less is provided.

  According to the ninth aspect of the present invention, there is provided a molded body obtained by thermoforming the biaxially stretched polypropylene sheet of any one of the first to eighth aspects.

  The biaxially stretched polypropylene sheet and molded product of the present invention can be widely used as packaged products in various fields such as foods, detergents and medical supplies as thermoformed products having excellent uniform stretchability and high commercial value.

It is a figure which shows an example of the molecular weight distribution curve in GPC of the propylene-type polymer (A) 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 (A) which concerns on this invention. 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 the propylene-type polymer (A) based on this invention.

The biaxially oriented polypropylene sheet of the present invention includes the following (i) to (vi), or in addition to them, (vii) and (viii), or in addition to them, (ix) and / or (x) Propylene polymer (A) having the characteristics and properties of 100 to 5% by weight and a propylene polymer (B) having a melting point of 150 to 170 ° C. measured by DSC and 0 to 95% by weight It is a biaxially stretched polypropylene sheet made of a resin composition.
Moreover, the biaxially stretched polypropylene sheet of the present invention includes the following (i) to (vi), or in addition to them, (vii) and (viii), or in addition to them, (ix) and / or ( x) The propylene polymer (A) having the characteristics and properties of 100 to 5 to 5% by weight and the propylene polymer (B) having a melting point measured by DSC of 150 to 170 ° C. and 0 to 95% by weight were blended. It is obtained by stretching an extruded sheet made of a propylene-based resin composition in the biaxial direction.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 to 20 g / 10 min.
(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.
(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.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.
(Vii) (MT230 ° C.) ≧ 5 g
[In the formula, MT230 ° C. is measured using a melt tension tester, capillary: diameter 2.1 mm, cylinder diameter: 9.6 mm, cylinder extrusion speed: 10 mm / min, winding speed: 4.0 m / min, temperature: 230 It represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [where, MaxDraw (maximum winding speed) is the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. Represent. ]
(Ix) (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. ]
(X) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0.

Hereinafter, the components of the propylene-based resin composition, the method for preparing the polypropylene-based resin composition, the biaxially stretched polypropylene sheet, and the like will be described in detail.
I. Components of propylene-based resin composition Propylene polymer (A)
The propylene-based polymer (A) constituting the propylene-based resin composition used for the biaxially stretched polypropylene sheet of the present invention is the above (i) to (vi), or in addition to them, (vii) and (viii) ), Or in addition to these, (ix) and / or (x) characteristics / properties.
Hereinafter, each item will be described sequentially.

(1) Definition of propylene polymer (A), long chain branched structure and identification method The propylene polymer (A) according to the present invention has controlled 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 (A) 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.
Regarding the branched structure, the present inventor has 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 a propylene-based polymer described later, one end of the polymer mainly has a propenyl structure by a special chain transfer reaction generally called β-methyl elimination. A so-called macromer is generated.
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 (A) 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 at 44.0-44.1 ppm, 44.7-44.8 ppm, and 44.8-44.9 ppm, respectively. Methine carbon (Cbr) is observed at ˜31.7 ppm. Hereinafter, the methine carbon observed at 31.6 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 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 31.6 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.

From the rheological point of view, the propylene polymer (A) showing improved melt properties according to the present invention needs to have a branch number of 0.01 or more.
Moreover, when there is too much quantity of branching, there exists concern that a gel will produce | generate and the external appearance of a molded article may be impaired. Furthermore, if the amount of branching is too large, there is a problem that when the melt is stretched at a high speed during molding, the melt breaks, that is, the so-called melt spreadability is deteriorated.
Therefore, the number of branches is preferably 0.4 or less, preferably 0.2 or less, and more preferably less than 0.1.
Even in the case of using the current ¹³ C-NMR of high magnetic field NMR, the measurement limit is 0.1 or more, and the quantification has not been reached so far. Note that the branch itself is evaluated as “trace” when it is detected.

In addition, the propylene polymer (A) according to the present invention is required 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 polymer (A) 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 (A) 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 polymer (A) according to the present invention, when the molecular weight of the macromer produced from the active species derived from [A-1] is 50,000 in number average molecular weight, the average molecular weight of the incorporated branched chain is There are 50,000, and it is interpreted as 2400 when converted into skeleton carbon.
The number average molecular weight of the macromer generated from the active species derived from the above [A-1] is based on the molecular weight when the polymerization is carried out by the peak top of the portion derived from [A-1] in GPC or [A-1] alone. Can be estimated.

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

Describing the relationship between the number of branches and the branch distribution, it is generally considered that a large number of branches is necessary in order to improve the melt properties. Japanese Patent Application Laid-Open No. 2007-154121 discloses that the number of branches is 0.1 / A propylene homopolymer having 1000 skeleton carbons or more is disclosed.
However, the degree of strain hardening in the measurement of the extensional viscosity is less than 6, and even when the degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene polymer (A) according to the present invention is 6.0 or more, it is improved. The effect is not enough. 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 (A) according to the present invention has an average number of branches of less than 0.1, but by introducing a branch also to the high molecular weight side by combining a plurality of complexes, the melt properties are improved. This is a significant improvement.

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 property of propylene polymer (A) The propylene polymer (A) in this invention is excellent in the balance of the physical property and melt processability which controlled melt fluidity and melt tension. The physical properties of the propylene polymer (A) will be described.

(2-1) Melt flow rate (MFR):
The propylene polymer (A) according to the present invention needs to have a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 kg of 0.5 to 20 g / 10 minutes.
The melt flow rate (MFR) of the propylene polymer (A) is 0.5 to 20 g / 10 minutes, preferably 0.5 to 15 g / 10 minutes, and is in the range of 0.9 to 10 g / 10 minutes. Is more preferable. When the MFR is in this range, the sheet formability of the original fabric is excellent.
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.

(2-2) Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC:
The propylene polymer (A) according to the present invention has a weight-average molecular weight (Mw) to number-average molecular weight (Mn) ratio, Mw / Mn (Q value) of 3 by gel permeation chromatography (GPC) measurement. It must be in the range of 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 8.0 or less, and more preferably 7.5 or less.

(2-3) Bias of molecular weight distribution obtained from GPC molecular weight distribution curve toward high molecular weight side:
In the molecular weight distribution curve obtained by GPC, the propylene-based polymer (A) according to the present invention has a common logarithm of the molecular weight corresponding to the peak position as Tp and a common logarithm of the molecular weight at a position where the peak height is 50%. 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. It is desirable that / β is greater than 0.9 and less than 2.0. Here, α / β is an index representing the deviation of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created 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 of the present invention means that the molecular weight distribution of the polymer obtained by uniform polymerization at a single active site is further spread to the higher molecular weight side.
In the propylene polymer (A) according to the present invention, α / β is desirably greater than 0.9, preferably 1.0 or more, and more preferably 1.1 or more. Since α / β is greater than 0.9 and the amount of the high molecular weight component is relatively sufficient, the melt tension and swell ratio are high, and the moldability is good.
Moreover, as for the propylene polymer (A) based on this invention, it is desirable that (alpha) / (beta) is less than 2.0, Preferably it is less than 1.7, More preferably, it is less than 1.6. When α / β is less than 2.0, the amount of the high molecular weight component does not increase excessively and the fluidity is good.
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.

(2-4) Ratio of components having a molecular weight (M) of 2 million or more in the molecular weight distribution curve by GPC:
In the molecular weight distribution curve obtained by GPC, the propylene-based polymer (A) according to the present invention has a ratio of components having a molecular weight (M) of 2 million or more to the total amount of the polymer (hereinafter, molecular weight M (≧ 2 million). ) Or W (may be abbreviated as 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.

The propylene polymer (A) 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 2%. 0.0% by weight or more. When W (2 million or more) is 0.4% by weight or more, a small amount of a component having a high molecular weight, especially a component having a very high molecular weight, is contained, the melt tension and swell ratio are high, and the moldability is good. Become. In addition, it is thought that this very high molecular weight component contains a branched component as described above.
The propylene polymer (A) 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% by weight. Is less than. When W (2 million or more) is less than 10% by weight, the fluidity is good, the formation of a gel due to a very high molecular weight component is suppressed, and the appearance of the molded product is also good. Moreover, when W (2 million or more) is less than 10% by weight, it is possible to prevent so-called deterioration of melt ductility that the melt breaks when stretched at a high speed during molding.

  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 in series) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

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

(2-5) Temperature rising elution fractionation with orthodichlorobenzene (ODCB) (TREF):
The propylene-based polymer (A) according to the present invention, in an elution curve obtained by temperature rising elution fractionation (TREF) measurement, the component eluting at a temperature of 40 ° C. or less needs to be 3.0% by weight or less, Preferably it is 2.0 weight% or less, More preferably, it is 1.0 weight% or less, Most preferably, it is 0.5 weight% or less. If the component eluting at a temperature of 40 ° C. or less is 3.0% by weight or less, the machine may have a decrease in crystallinity of the entire product or a product rigidity due to a low crystalline component eluted at a temperature of 40 ° C. or less. The decrease in the mechanical strength can be suppressed.

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

The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions.
Spectral assignments were made with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30 pages 1350 (1989).

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

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

  Moreover, the propylene polymer (A) 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 (i), structure (ii), structure (iii), and structure (iv).

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 (38.7 ppm) in the position irregular substructure [structure (i)]. It can be evaluated from 1/4 of the sum of the peak areas of resonance in the vicinity.
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 (34.1 ppm) in the position irregular substructure [structure (ii) and structure (iii)]. It can be evaluated by 2/5 of the sum of the peak areas of resonance in the vicinity and the sum of the peak areas of carbon K (resonance at around 33.7 ppm).
The peak area based on carbon A ″ can be evaluated by the sum of the peak areas of carbon L (resonance at around 27.7 ppm).
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 (A) according to the present invention needs to have a strain hardening degree (λmax) of 6.0 or more in the measurement of elongational viscosity.
The strain hardening degree (λmax) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. 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.

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 (A) 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 of the present invention is replaced with 11,000 or more, preferably 21,000 or more, more preferably 42,000 or more in terms of number average molecular weight (Mn) measured by GPC. Can be considered.

  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 Seisakusho, Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: An extruded strand is prepared at a speed of 10 to 50 mm / min using an orifice having an inner diameter of 3 mm at 180 ° C. using a capilograph manufactured by Toyo Seiki Seisakusho.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain becomes 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity.
FIG. 4 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The 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):
In the propylene polymer (A) according to the present invention, the memory effect (ME) preferably satisfies the following formula (I-1).
(ME) ≧ −0.26 × log (MFR) +1.9 (I-1)
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

The propylene-based polymer (A) according to the present invention preferably has a correlation between a memory effect (ME) serving as an index representing the abundance ratio of a high molecular weight component in a polymer and MFR serving as an index representing an average molecular weight of the polymer. It is in 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 (A) according to the present invention has a large ME in MFR match as compared with a conventionally known polymer as shown in FIG. 5 due to the presence of a branched component in the polymer chain. It is a feature. 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) 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. The load is adjusted so as to be / min., And at that speed, the polymer extruded from the orifice is rapidly cooled 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 (A) according to the present invention has a controlled branch structure (branch amount, branch length, branch distribution), 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 the Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., the tension detected by the pulley when the resin is extruded in a string shape under the following conditions and wound on a roller is defined as melt tension (MT).
Capillary: 2.1mm in diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 230 ° C.

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

In addition, as described above, increasing the high molecular weight component or increasing the number of branches can increase the MT value, 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 (A) 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.
Therefore, the propylene polymer (A) according to the present invention has a MaxDraw of preferably 10 m / min or more, more preferably 20 m / min or more, and further preferably 30 m / min or more.

(3) Propylene Polymer (A) Production Method About the method of producing the propylene polymer (A) 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 (1), and at least one from component [A-2] which is a compound represented by general formula (2) Two or more types of transition metal compounds selected from Group 4 of the periodic table Component [A-1]: Compound represented by general formula (3) Component [A-2]: Represented by general formula (4) 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 the general formula (3)

[In General Formula (3), R ¹¹ and R ¹² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. R ¹³ and R ¹⁴ each independently represent halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a C 6-16 aryl that may contain a plurality of hetero elements selected from these. Represents a heterocyclic group containing nitrogen, oxygen or sulfur having 6 to 16 carbon atoms. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably 2-furyl group, substituted 2-furyl group, substituted 2-thienyl group, substituted 2-furfuryl group, more preferably a substituted 2-furyl group.
Examples of the substituted 2-furyl group, substituted 2-thienyl group, and substituted 2-furfuryl group include alkyl groups 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.

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

In the general formula (3), X ¹¹ and Y ¹¹ are auxiliary ligands, and react with the co-catalyst of the component (B) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited to the type of ligand, and are independently hydrogen, halogen groups, hydrocarbon groups having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In the general formula (3), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms silylene 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 (3), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4- Enyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-methyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4-isopropyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-Methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4 -(4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, and the like. .

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

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

(Ii) Component [A-2]: Compound represented by the general formula (4)

[In General Formula (4), 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. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ²³ and R ²⁴ each independently contain a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluoro-4-biphenyl), 4- (2-chloro-4-biphenyl), 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.

The following can be mentioned as a non-limiting example of the metallocene compound represented by the general formula (4).
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-biphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (2-chloro-4-biphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazulenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl-] 4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, 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-biphenyl) -4-hydroazurenyl}] hafnium, Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9 -Diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethyl Tylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) ) -4-Hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4 -Hydroazulenyl}] 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-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -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}] Hough 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-biphenyl) -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 (A) 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 diameter, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in component (B).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product. You may include them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other 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 treatment 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 component (B).
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the component (B) after removal is 3% by weight or less, preferably 0% by weight when the water content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. Is preferably 1% by weight or less.

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

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

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

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

(C) Catalyst component (C)
The catalyst component (C) used for the polymerization of the propylene-based polymer (A) according to the present invention is an organoaluminum compound. As the organoaluminum compound used as the component (C), a compound represented by the general formula: (AlR ¹⁵ _q Z _3-q ) _p is appropriate.
In this invention, it cannot be overemphasized that the compound represented by this formula can be used individually, in mixture of multiple types, or in combination. In this formula, R ¹⁵ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively. R ¹⁵ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, and a C 1 atom when it is an amino group. Eight amino groups are preferred.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, R ¹⁵ 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 the (preliminary) polymerization tank simultaneously or continuously, or once or several times. Can do.
The contacting of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When using component (C), before contacting component (A) with component (B), component (A), or component (B), or both component (A) and component (B) The component (C) is contacted, or the component (A) and the component (B) are contacted at the same time as the component (C) is contacted, or the component (A) and the component (B) are contacted. Although it is possible to contact the component (C) later, a method of contacting the component (C) with any of the components (A) and the component (B) is preferable.
Moreover, after making each component contact, it is possible to wash | clean with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

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

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

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

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

  In addition, a method in which a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania is allowed to coexist during or after the contact of each component described above is also possible.

(E) Use of Catalyst / Propylene Polymerization Any polymerization method may be used as long as the olefin polymerization catalyst including the component (A), the component (B) and the component (C) is in efficient contact with the monomer. obtain.
Specifically, a slurry method using an inert solvent, a so-called bulk method, a solution polymerization method, or a substantially liquid solvent without using an inert solvent as a solvent. 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, multistage polymerization of two or more stages is also possible.

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, more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, it is preferably 40 ° C or higher, more preferably 50 ° C or higher. 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 2.0 MPa or more is more preferable. The upper limit is preferably 2.5 MPa or less, more preferably 2.0 MPa or less.

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

In addition to the propylene monomer, copolymerization using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer may be performed. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and a plurality of the above-mentioned comonomers can be used. Specifically, they are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.
Among these, in order to obtain the propylene polymer (A) 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 particular, in order to obtain a polymer having high rigidity, it is preferable to use ethylene so that ethylene contained in the polymer is 1 mol% or less, and propylene homopolymerization is more preferable.

(F) Consideration of polymerization mechanism It is considered that the formation of a macromer is caused by a special chain transfer reaction generally called β-methyl elimination. In the present invention, the component [A-1] having a specific structure is relatively In the low temperature range (40 ° C. to 80 ° C.), the selectivity of the β-methyl elimination reaction during the growth termination reaction is high, and the ratio of the β-methyl elimination reaction to the polymer growth reaction is higher than that of the complex having the conventional structure. It has been found that it is large in comparison.
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 (A) production method is characterized by a small change in the balance between macromer formation and growth reaction even when hydrogen is added, and the macromer selectivity is hardly changed 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 further compared to the component [A-1]. And has the ability to produce higher molecular weight polymers. Further, when hydrogen is added, the activity is improved, and the molecular weight is lowered due to chain transfer by hydrogen.
Conventionally, macromer formation and macromer copolymerization are produced by a single complex, that is, in order to produce a polymer with the same complex of component [A-1] and component [A-2], If either the capacity or the macromer copolymerization capacity is insufficient, the amount of branching component introduced is insufficient on the high molecular weight side, or if hydrogen is used to adjust the molecular weight, the production amount of the macromer itself decreases. There was a problem of doing.

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

(2) Polymerization Method of Propylene Polymer (B) The propylene polymer (B) used in the present invention is a solid catalyst component (a) containing titanium, magnesium and halogen as essential components as a catalyst used for polymerization. ) And an organoaluminum component (b). Further, it is more preferable that a Ziegler-Natta catalyst formed from a solid catalyst component (a) having an essential component of titanium, magnesium, halogen and an electron donor and an organoaluminum component (b) is used for the polymerization. .

Furthermore, it is preferable to use the solid catalyst component (a) obtained by contacting the following (i), (ii), (iii) and (iv).
(I) Solid component containing titanium, magnesium and halogen as essential components (ii) Organic containing two or more Si—OR ¹ bonds (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) Silicon compound (iii) Vinylsilane compound (iv) Organometallic compound of Group I to III metals

<Component (i)>
Component (i) is a raw material solid component containing titanium, magnesium and halogen. These three elements (three components) of titanium (Ti) -magnesium (Mg) -halogen are contained as essential components. Here, “contained as an essential component” means that in addition to the listed three components, other suitable elements may be included, and each of these elements is present as an arbitrary desired compound. As well as the fact that these elements may exist as bonded to each other. The raw material solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45688
, 54-3894, 54-31092, 54-39483, 54-94591, 54-118484, 54-131589, 55-75411, 55-90510, 55-90511, 55-90511, 55-127405, 55-147507, 55-155003, 56-18609, 56-70005, 56-72001, 56 -86905, 56-90807, 56-155206, 57-92007, 57-12003, 58-5309, 58-5310, 58-5311, 58-8706 58-27732, 58-32604, 58-32605, 58-67703, 58-117206 58-127708, 58-183708, 58-183709, 59-149905, 59-149906, 60-130607, 61-55104, 61-204204, 62-508, 62-15209, 62-20507, 62-184005, 62-236805, 63-199207, 63-264607, 63-264608, JP-A-1 -79203, 1-139601, 1-215806, 7-258328, 7-269125, 11-21309, each publication, etc. are used.

  Moreover, the thing etc. which processed these with tungsten and a molybdenum compound are mentioned.

  Examples of the magnesium compound serving as the magnesium source of component (i) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. Of these, preferred are magnesium halide, dialkoxymagnesium and alkoxymagnesium halide.

Further, the titanium compound serving as a titanium source component (i) has the general formula _{^{Ti (OR 2) 4-q}} X q ( where, ^{R 2} is a hydrocarbon group, preferably of the order of 1 to 10 carbon atoms Yes, X represents halogen, and q is 0 ≦ q ≦ 4.) Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-i-C _{3). H 7) Cl 3, Ti (} O-n-C 4 H 9) Cl 3, Ti (O-n-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (OC 2 H _{5) (O-n-C} 4 H 9) 2 Cl, Ti (O-n-C 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-i-C 4 H 9) ₂ Cl ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O— _{n-C 4 H 9) 4} , Ti (O-i-C 4 H 9) 4, Ti (O-n-C 6 H 13) 4, Ti (O- _{-C 8 H 17) 4, Ti} (OCH 2 CH (C 2 H 5) C 4 H 9) 4 , and the like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ is a halogen) can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.

In addition, TiCl ₃ (including those obtained by reducing TiCl ₄ with hydrogen, those reduced with aluminum metal, or those reduced with an organometallic compound), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride and cyclopentadienyl titanium trichloride.

Among these titanium compounds described above, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are particularly preferable.

The halogen of component (i) is usually supplied from the aforementioned magnesium and / or titanium halogen compounds, but other halogen sources, for example, aluminum halides such as AlCl ₃ , boron such as BCl _3, etc. Supplied from known halogenating agents such as halides of silicon, silicon halides such as SiCl ₄ , phosphorus halides such as PCl ₃ and PCl ₅ , tungsten halides such as WCl ₆ , molybdenum halides such as MoCl ₅ You can also The halogen contained in the solid catalyst component (a) may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  Examples of the electron donor (internal donor) that can be used for the production of the raw material solid component (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, Examples include oxygen-containing electron donors such as acid amides and acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonate esters. it can.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ) Phenols having 6 to 25 carbon atoms which may have alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones such as benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, Aldehydes of 2 to 15 carbon atoms such as naphthaldehyde,

(E) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate , Organic acid monoesters such as methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide Or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane C2-C20 organic acid esters of organic acid polyvalent esters such as -1,2-dicarboxylic acid-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate,

(F) Carbon number of inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride 2-15 acid halides, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-t-butyl-2- Til-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3- 2-20 carbon atoms such as dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane Ethers of

(Li) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine , Nitriles such as (l) acetonitrile, benzonitrile, tolunitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy-2-phenylpropiyl Alkoxy ester compounds such as ethyl onate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate,

(Wa) Ketoester compounds such as ethyl 2-benzoylbenzoate, ethyl 2- (4′-methylbenzoyl) benzoate, ethyl 2-benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, benzene Examples thereof include sulfonic acid esters such as ethyl sulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate.

Two or more kinds of these electron donors can be used.
Among these, organic acid ester compounds, acid halide compounds and ether compounds are more preferable, and particularly preferable are those selected from the group consisting of phthalic acid diester compounds and phthalic acid dihalide compounds.

The solid catalyst component (a) is produced, for example, by the following production method using other components as necessary.
(A) A method of contacting a magnesium halide with an electron donor and a titanium-containing compound.
(B) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and a magnesium halide, an electron donor, and a titanium halogen-containing compound are brought into contact therewith.

(C) Inert reaction products obtained by contacting a titanium halide compound and / or a silicon halogen compound and an electron donor with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound. A method of washing with an organic solvent. In addition, as a polymer silicon compound used here, what is shown by a following formula is suitable.
-[Si (H) (R ³ ) -O-] _X-
Here, in the above formula, R ³ is a hydrocarbon group having about 1 to 10 carbon atoms, and x represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.
Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 , 9-pentamethylcyclopentasiloxane is preferred.

(D) A magnesium compound is dissolved with a titanium tetraalkoxide and / or an electron donor, and the titanium compound and the electron donor are brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. How to contact.
(E) An organomagnesium compound such as a Grignard reagent is allowed to act on a halogenating agent, a reducing agent, etc., and then contacted with an electron donor as necessary, and then contacted with a titanium compound and an electron donor , How to contact each one separately.
(F) A method in which an alkoxymagnesium compound is contacted with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor, or each is contacted separately.

  Among these production methods, the above (a), (c), (d) and (f) are particularly preferable.

<Component (ii)>
The component (ii) preferably used for producing the solid catalyst component (a) of the present invention contains two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms). It is an organosilicon compound.

As bond residues other than —OR ¹ group bonded to a silicon atom, a bond residue selected from hydrogen, halogen, a hydrocarbon group (for example, an alkyl group, a cycloalkyl group, an aryl group, etc.) and a siloxy group What you have is usually used.

  Preferred organosilicon compounds are those having at least one hydrocarbon group, more preferably a carbon atom adjacent to the silicon atom, that is, the α-position hydrocarbon atom is a secondary or tertiary carbon atom and has 3 carbon atoms. It has -20 branched chain hydrocarbon groups.

Specific examples of the organosilicon compound of component (ii) include (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₃ H ₇ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₆ H ₁₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C _{2 H 5) CHSi (CH 3} ) (OCH 3) 2, ((CH 3) 2 CHCH 2) 2 Si (OCH 3) 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH _{3) 2, (C 2 H} 5) (CH 3) 2 CSi (C _{3) (OC 2 H 5)} 2, (CH 3) 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H 5) 3, (CH 3) (C 2 H 5) CHSi (OCH 3 ) ₃ , (CH ₃ ) ₂ CH (CH ₃ ) ₂ CSi (CH ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₃ C) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ , ( (CH ₃ ) ₂ CH) ₂ Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (C _{5 H 9) 2 Si (OC 2} H 5) 2, (C 5 H 9) (CH 3) S _{(OCH 3) 2, (C} 5 H 9) ((CH 3) 2 CHCH 2) Si (OCH 3) 2, (C 6 H 11) Si (CH 3) (OCH 3) 2, (C 6 H 11 ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ((CH ₃ ) ₂ CHCH ₂ ) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) ((C ₂ H ₅ ) (CH ₃ ) CH) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) ((CH ₃ ) ₂ CH) Si (OC ₅ H ₁₁ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si ( _{CH 3) (OCH 3) 2} , HC (CH 3) 2 C (CH 3) 2 Si (CH 3) (OC 2 H 5) 2, HC (CH 3) 2 C (CH 3) 2 Si (OCH 3 _{) 3, (CH 3) 3} CSi (OCH (CH 3) 2) (O H _{3) 2,} include ₂ or the like _{(CH 3) 3 CSi (OC} (CH 3) 3) (OCH 3).

Among these, preferred are (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₃ H ₇ ) (OCH _{3 ) 2, (CH 3) 3} CSi (n-C 6 H 13) (OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 Si (OC 2 H 5 ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) _{2 and the} like.

<Ingredient (iii)>
Component (iii) preferably used to form solid catalyst component (a) is a vinyl silane compound. As the vinylsilane compound, at least one hydrogen atom in monosilane (SiH ₄ ) is replaced with a vinyl group (CH ₂ ═CH—), and some of the remaining hydrogen atoms are halogen (preferably Cl), It shows a structure substituted with a hydrocarbon group (preferably an alkyl group having 1 to 12 carbon atoms), an aryl group (preferably a phenyl group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), or the like. is there.

More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5), (CH 2 = CH) 2 -SiH 2, (CH 2 = CH) 2 -SiH (CH 3), (CH _{2 = CH) 2 -SiH (CH} 3), (CH 2 = CH) _{-Si (CH 3) 2, (} CH 2 = CH) 2 -SiCl 2, (CH 2 = CH) 2 -SiCl (CH 3), (CH 2 = CH) 2 -SiH (Cl), (CH 2 = _{CH) 2 -Si (C 2 H} 5) 2, (CH 2 = CH) 2 -SiCl (C 2 H 5), (CH 2 = CH) 2 -Si (CH 3) (C 2 H 5), ( _{CH 2 = CH) 3 -SiH,} (CH 2 = CH) 3 -Si (CH 3), (CH 2 = CH) 3 -SiCl, (CH 2 = CH) 3 -Si (C 2 H 5), ( CH ₂ ═CH) ₄ —Si and the like can be exemplified. Of these, CH ₂ ═CH—Si (CH ₃ ) ₃ and (CH ₂ ═CH) ₂ —Si (CH ₃ ) ₂ are particularly preferable.

<Component (iv)>
Component (iv) preferably used to form the solid catalyst component (a) is an organometallic compound of periodic group I-III. Since it is an organometallic compound, this compound has at least one organic group / metal bond. The organic group in that case is typically a hydrocarbon group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms. Typical metals for this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group is a hydrogen atom, a halogen atom, a hydrocarbon group (the hydrocarbon group has 1 to 10, (specifically, methylalumoxane -O-Al _(CH 3) preferably having about 1 to 6 is), or the metal through a carbon atom -), is satisfied otherwise.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tert-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium and butylmagnesium. Organic magnesium compounds such as chloride and tert-butylmagnesium bromide, (c) Organic zinc compounds such as diethylzinc and dibutylzinc, (d) Trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n -Octyl aluminum, tri-n-decyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride Diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, and organic aluminum compounds such as methylaluminoxane.
Of these, organoaluminum compounds are particularly preferred.

<Production of solid catalyst component (a)>
The solid catalyst component (a) is obtained by bringing the components (i) to (iv) constituting the component (a) and optional components used as necessary into contact with each other step by step or temporarily. And / or finally by washing with an organic solvent.
Specifically, (a): a method in which the component (i) and the component (iii) are contacted, then the component (ii) and the component (iv) are contacted, and finally washed (b): the component ( Method of contacting and washing component (iii) and component (iv) after contacting i) and component (ii), (c): contacting component (i), (ii), and (iii) simultaneously Later, a method of bringing component (iv) into contact and washing is employed.

  As the solvent used for the organic solvent washing, an inert organic solvent, for example, an aliphatic or aromatic hydrocarbon solvent (for example, hexane, heptane, toluene, cyclohexane, etc.), or a halogenated hydrocarbon solvent (for example, chloride-n-) is used. Butyl, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

Although the contact conditions of each component constituting the solid catalyst component (a) need to be carried out in the absence of oxygen, it can be arbitrary as long as the effect of the present invention is recognized. The following conditions are preferred.
The contact temperature is about −50 to 200 ° C., more preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, and the like, and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes, and the like.

The amount ratio of each component used to constitute the solid catalyst component (a) can be any as long as the effect of the present invention is recognized, but generally it is preferably within the following range.
The usage-amount of the titanium compound of a component (i) is 0.0001-1,000 by mole ratio (Ti / Mg) with respect to the usage-amount of the magnesium compound to be used, More preferably, it is 0.01-10. When a compound therefor is used as the halogen source, the amount used is 0.01 by mole relative to the amount of magnesium used, regardless of whether the titanium compound and / or magnesium compound contains halogen. -1,000 is good, and more preferably is 0.1-100. The amount of the electron donor used is 0.001 to 10 in molar ratio (halogen / Mg) to the amount of magnesium compound used, and more preferably 0.01 to 5.

The quantity ratio of component (i) to component (ii) is 0.01 to 1,000, more preferably the atomic ratio (silicon / titanium) of silicon of component (ii) to the titanium component constituting component (i). 0.1-100. The quantity ratio of the component (iii) to the component (i) is 0.01 to 1,000 in terms of the atomic ratio (silicon / titanium) of the silicon atom in the component (iii) to the titanium atom in the component (i). Preferably it is 0.01-300. The amount of the organometallic compound of component (iv) used is 0.1 to 100, more preferably 1 to 50 in terms of the atomic ratio of metal to the titanium component constituting component (i) (metal atom / titanium).
In the middle and / or at the end of the production of the solid catalyst component (a), a washing step with an inert organic solvent similar to that used in the solvent washing may be added in addition to the solvent washing. it can.

  The organoaluminum component (b) is used as a co-catalyst, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diisobutylaluminum chloride, diethylaluminum hydride and the like Alkyl aluminum hydrides, alkylaluminum alkoxides such as diethylaluminum ethoxide, alumoxanes such as methylalumoxane and tetrabutylalumoxane, reaction products of trialkylaluminum and dibutyl methylboronate, and composite organoaluminum compounds such as lithium aluminum tetraethyl It is done. It is also possible to use a mixture of two or more of these.

  The amount of the propylene polymer (A) is in the range of 100 to 5% by weight, preferably in the range of 100 to 20% by weight, more preferably in the range of 100 to 50% by weight, and in the range of 100 to 70% by weight. More preferably, the range of 100 to 80% by weight is particularly preferable, and the range of 100 to 90% by weight is most preferable. If the blending amount of (A) is less than the above, uniform stretchability is inhibited.

As a polymerization method of the propylene polymer (B) of the present invention, in the presence of the catalyst, a slurry method using an inert solvent, a solution method, a gas phase method substantially using no solvent, or a polymerization monomer And a bulk polymerization method using as a solvent. As a method for obtaining the propylene-based polymer (B) used in the present invention, for example, a desired polymer can be obtained by adjusting the polymerization temperature and the comonomer amount and appropriately controlling the molecular weight and the crystallinity distribution. .
Such a propylene polymer (B) can be appropriately selected from those commercially available as polypropylene and used. Examples of commercially available products include “NOVATEC” manufactured by Nippon Polypro Co., Ltd.

It is preferable to use an electron donating compound (external donor) at the time of production. Examples of the electron donating compound (external donor) include those exemplified as the electron donating compound (internal donor) in the solid component (i), and organic silicon containing two or more Si—OR ¹ bonds exemplified in the component (ii). A compound etc. can be illustrated.
Among these, in particular, when tert-butylmethyldimethoxysilane is used as an external donor at the time of production, the isotactic pentad fraction (mmmm fraction) of the propylene-based polymer is further increased and the rigidity is improved.

  The catalyst system comprising the solid catalyst component (a) and the organoaluminum component (b) is characterized in that the melt flow rate varies greatly depending on the amount of hydrogen that is a chain transfer agent.

The polymerization is preferably performed by multistage polymerization in which raw material propylene (and ethylene is the same hereinafter) is polymerized in a gas phase.
Each step of the gas phase polymerization step may have any number of steps.

  The polymerization reactor is not particularly limited in shape and structure, and examples thereof include a fluidized bed reactor and a horizontal reactor having a stirring blade.

  In addition to a single polymerization tank, two or more tanks connected in series are used. The solid catalyst component (a) is supplied only to the first polymerization tank, and most of the organoaluminum component (b) is supplied to the first polymerization tank. It does not matter.

  In the first polymerization tank, a predetermined amount of propylene is continuously supplied at a constant polymerization pressure and temperature, and the catalyst and hydrogen are controlled so that the ratio of propylene to hydrogen is constant. The produced polymer is sequentially transferred to the next stage polymerization tank together with the unreacted raw material. No catalyst is supplied to the second and subsequent polymerization tanks, and polymerization is carried out with the catalyst contained in the polymer transferred from the preceding polymerization tank. Further, in the second and subsequent polymerization tanks, the supply of propylene is continued so that the polymerization pressure is maintained at a predetermined value. Hydrogen may or may not be supplied after the second polymerization tank. When not supplied, the hydrogen remaining as unreacted in the preceding polymerization tank is transferred to the next reactor and used.

Although it does not specifically limit regarding the polymerization pressure, Usually, 0.2-5 Mpa, Preferably it implements at about 0.3-2 Mpa. The polymerization pressure in each stage may be the same or different.
The polymerization temperature is not particularly limited, but is usually selected from the range of 20 to 100 ° C, preferably 40 to 80 ° C. The polymerization temperature in each stage may be the same or different.

The polymerization time is not particularly limited, but is usually 10 minutes to 10 hours.
In addition, the polymerization time of each stage of the multistage is not particularly limited, but is set to 30 minutes for the first stage, 30 minutes for the second stage, and 1 hour for the third stage.

The propylene polymer (B) has a melting point measured by DSC of 150 to 170 ° C, and preferably in the range of 155 to 165 ° C. When the melting point is below this range, the rigidity of the sheet is lowered, and when it is above, the transparency is lowered.
The blending amount of (B) is in the range of 0 to 95% by weight, preferably in the range of 0 to 80% by weight, more preferably in the range of 0 to 50% by weight, still more preferably in the range of 0 to 30% by weight, A range of 0 to 20% by weight is particularly preferred, and a range of 0 to 10% by weight is most preferred. If the blending amount of (B) exceeds the above, uniform stretchability is inhibited.

  In the present invention, the stretching ratio of the stretched sheet is preferably 1.5 times or more for both MD / TD, the surface ratio is preferably 3 to 30 times, the surface ratio is more preferably 5 to 25 times, and 7 to 20 times. Stretching is more preferable. If the surface magnification exceeds the above, it is necessary to increase the thickness of the original sheet, and it may be difficult to handle the sheet forming and stretching processes with the existing equipment.

In the present invention, it is more preferable that a nucleating agent represented by the following general formula (1) is blended. The preferable compounding amount is 0.1 to 1% by weight of the nucleating agent with respect to 100% by weight of the polymer mixture (propylene polymer (A) + (B)). 0.2-1 weight% is more preferable and 0.2-0.8 weight% is further more preferable.
When the blending amount of the nucleating agent is 0.1% by weight or more, the effect of improving the transparency is sufficient, and when it is 1% by weight or less, it is advantageous from the viewpoint of the cost (the cost / performance).

  As the nucleating agent, a nucleating agent represented by the following chemical formula (1) is used.

［但し、式（１）中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、炭素数が２〜２０のアルケニル基、炭素数が１〜２０のアルコキシ基、カルボニル基、ハロゲン基またはフェニル基であり、Ｒ６は、水素原子または炭素数が１〜２０のアルキル基である。］

[In the formula (1), n is an integer of 0 to 2, and R1 to R5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. An alkenyl group, an alkoxy group having 1 to 20 carbon atoms, a carbonyl group, a halogen group or a phenyl group, and R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

A commercially available nucleating agent can be used. For example, trade name “Gelall MD” manufactured by Shin Nippon Chemical Co., Ltd., trade names “Mirad 3988” and “Mirad NX8000J” manufactured by Milliken, etc. may be mentioned, with Mirad NX8000J being most preferred.
These nucleating agents may be used in combination of two or more.

In addition, the propylene polymer used in the present invention includes an antioxidant, a neutralizing agent, a nucleating agent, a light stabilizer, an ultraviolet absorber, an inorganic filler, an antiblocking agent, a lubricant, an antistatic agent, and a metal inertness. Various additives that can be usually used for polypropylene, such as an agent, a peroxide, and a colorant, 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, zinc stearate, and aluminum stearate. And hydrotalcites, and examples of light stabilizers and ultraviolet absorbers include hindered amines, nickel complex compounds, benzotriazoles, and benzophenones.
The propylene polymer composition can be used alone as it is, or in a range not impairing the effects of the present invention, other polypropylenes different from the propylene polymers (A) and (B), polyethylene, Another polymer such as an elastomer or a petroleum resin can be added and used.

  The propylene-based polymer used in the present invention is a polypropylene-based resin composition in which predetermined amounts of the above-described nucleating agent, various additives, and another polymer are blended as necessary. It can also be used for production and is a preferred form of the present invention. Polypropylene-based resin compositions are blended or melted with these compounding ingredients such as Henschel mixer (trade name), super mixer, V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, uniaxial or biaxial extruder. It can be prepared by mixing or melt-kneading in a kneader.

[Biaxially stretched polypropylene sheet]
The biaxially stretched polypropylene sheet of the present invention is a sheet composed of a main layer containing at least the polypropylene resin composition of the present invention, and may have a multilayer structure of two or more layers. For example, even if a barrier sheet in which a barrier resin layer such as ethylene-vinyl alcohol copolymer (EVOH) or polyamide resin and an adhesive layer are provided on at least one surface of the main layer, a high gloss layer or low It is also possible to arrange a layer having a design property such as a glossy layer.
In addition, a surface treatment agent such as an antifogging agent, an antistatic agent, or a lubricant can be applied to one side and both sides of the sheet.

The biaxially stretched polypropylene sheet of the present invention is produced by supplying the polypropylene resin composition to a known extruder, melting it, and cooling and solidifying the unstretched sheet in a biaxial direction.
A known method can be used to manufacture the unstretched sheet. For example, a method in which a resin melt-extruded from a T die is wound around a cooling roll, or a method in which a resin melt-extruded from a circular die is cooled and solidified by air cooling or water cooling is used. Can be mentioned.
As the stretching method, a known method can be used, and examples thereof include a tenter-type stretching method, a roll stretching method using a speed difference between rolls, and a pantograph batch stretching method.
The thickness of the raw fabric sheet using the polypropylene resin composition used in the present invention is preferably 1 to 4 mm, more preferably 1.5 to 3.5 mm, and particularly preferably 1.8 to 3 mm. When the thickness is 1 mm or more, it becomes easy to ensure the thickness of the sheet after stretching, and when the thickness is 4 mm or less, the sheet is easily formed.

The raw sheet of the propylene polymer mixture can be formed into a multi-layer polypropylene sheet using a feed block or a multi-manifold using a plurality of extruders usually used for forming polypropylene in addition to a single layer. it can.
As a specific method for producing a polypropylene-based sheet, a polypropylene-based resin composition in which other components (nucleating agent, various additives, other polymers) are blended with the polypropylene-based resin composition as necessary may be a known uniaxial or After passing through a twin screw extruder and extruding from a coat solder die into a sheet, air knife, air chamber, hard rubber roll, steel belt on the metal roll surface (with cooling water and oil circulating inside) It can be obtained by pressing with a metal flex roll or metal roll and solidifying by cooling. It is also possible to cool and solidify both sides of the sheet with a steel belt.
Among such sheet cooling methods, the method using a metal roll and / or a steel belt and a metal flex roll on both sides of the sheet is most advantageous because a sheet surface with less surface irregularities, that is, a sheet having excellent transparency can be obtained. This is the preferred method.

[Molded body]
The molded product of the present invention is a molded product thermoformed using the biaxially stretched polypropylene sheet of the present invention.
One aspect of the molded body of the present invention is a molded body that is vacuum-pressure molded using the biaxially stretched polypropylene sheet of the present invention at a pressure lower than the melting peak temperature and at a pressure of 0.2 MPa or more.

  Examples of the heating method in such thermoforming include indirect heating, hot plate heating, and hot roll heating. When the molding is performed at a temperature exceeding the melting peak temperature of the sheet, the transparency, gloss, and thickness uniformity of the resulting molded article are deteriorated and the molding tends to be impossible.

When thermoforming is carried out below the melting peak temperature of the crystalline propylene polymer, it is preferably softened by heating at a temperature within the melting peak temperature range of 5 to 30 ° C., from the mold cavity side. It can shape | mold by vacuum-sucking and applying the pneumatic pressure of 0.2 Mpa or more from the other side, and making this biaxially-stretched polypropylene-type sheet closely_contact | adhere to the mold cavity surface.
If the pressure pressure exceeds 0.2 MPa, the shape of the mold can be easily obtained. The pneumatic pressure is 0.2 MPa or more, preferably 0.3 MPa or more, more preferably 0.35 MPa or more.
Also, an assist plug can be provided, which is preferable because the thickness uniformity of the molded body is improved.

[Use of molded body]
Since the molded article of the present invention is excellent in design and can be heated in a microwave oven, it can be widely used in products in various fields such as food packaging lids, food containers, detergent containers, and medical containers.

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

1. Evaluation method (1) Melt flow rate (MFR) [unit: g / 10 min]
The propylene-based resin conforms to JIS K7210: 1999 “Method for testing plastics-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR)”, condition M (230 ° C., 2.16 kg load). The ethylene / α-olefin copolymer was measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-2: 1997 appendix.
(2) Melting point (Tm) and crystallization temperature (Tc)
Using a Seiko Instruments DSC6200, the sheet-shaped sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. The crystallization temperature (Tc) is obtained as the maximum crystal peak temperature (° C.) when the temperature is lowered to 20 ° C., and then the maximum melting peak when the temperature is increased to 200 ° C. at 10 ° C./min. The melting point (Tm) was determined as the temperature (° C.).
(3) Molecular weight and molecular weight distribution (Mw / Mn, molecular weight M (≧ 2 million), α / β)
Measurement and calculation were performed by gel permeation chromatography (GPC) by the method described in the present specification.
(4) Elevated temperature elution fractionation (TREF)
The TREF measurement method is as described above 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) MT (Melt Tension) and Maximum Winding Speed Using Capillograph 1B manufactured by Toyo Seiki Seisakusho 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. Measured as melt tension (MT).
Capillary: 2.1mm in diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 230 ° C.
Further, when the winding speed is gradually increased from 4.0 m / min (acceleration: 5.4 cm / s ² ), the winding speed immediately before the string-like material is cut is defined as the maximum winding speed (MaxDraw). It was measured.
(6) ME (memory effect)
Using a melt indexer manufactured by Takara Co., Ltd., at 190 ° C., with an orifice diameter of 1.0 mm and a length of 8.0 mm, extruding with a load, adjusting the load so that the extrusion speed becomes 0.1 g / min, At that speed, the polymer extruded from the orifice was quenched in ethanol, and the strand diameter at that time was divided by the orifice diameter. This value correlates with Log (MFR), and a large value indicates that the product appearance is improved when the swell is large and injection molded.
(7) mm fraction Measured by the method described in the present specification using GSX-400, FT-NMR manufactured by JEOL Ltd. The unit is%.
(8) Measurement of ethylene content
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.
(9) Elongation viscosity Measured by the method described in the present specification.
(10) Composition analysis A calibration curve was prepared by chemical analysis by the JIS method and measured by fluorescent X-ray.

(11) Standard deviation It was measured according to any of the following evaluation methods.
In the center of the surface of the unstretched original fabric sheet cut to 95 mm square, a grid is stamped at 10 mm intervals within a 50 mm square, and biaxially stretched using a biaxial stretching machine (biaxial stretching test device manufactured by Toyo Seiki Seisakusho). (Manufacturing-1) The intersection thickness (25 intersection points) of the stretched board was measured, and the standard deviation value of the thickness was obtained. The draw ratio was longitudinal direction × lateral direction = 4 × 4 times (area magnification = 16 times).
In the center of the surface of the unstretched original fabric sheet cut to 95 mm square, a grid is stamped at intervals of 10 mm within a 50 mm square, and biaxially stretched using a biaxial stretching machine (KAROIV manufactured by Bruckner) (Production-2). The crossing thickness (25 crossing points) of the stretched board was measured, and the standard deviation value of the thickness was obtained. The draw ratio was longitudinal direction × lateral direction = 3 × 3 times (area magnification = 9 times).

2. Materials used [1] Propylene polymer (A)
The propylene-based resin (PP-1) and propylene-based resin (PP-2) produced in the following Production Examples 1 and 2 were used.

Production Examples of Propylene Resin (PP-1) and Propylene Resin (PP-2) [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 In 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, 0.20 mol) was gradually added thereto, followed by stirring 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 In a 1000 ml glass reaction vessel, methyl furan (13.8 g, 0.17 mol) Dimethoxyethane (400 ml) was added 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 In a 1000 ml glass reaction vessel, 4- (4-t -Butylphenyl) -2- (5-methyl-2-furyl) -indene (22 g, 66 mmol) and THF (200 ml) were added and cooled to -70 ° C. 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 500 ml glass 9.6 g (13.0 mmol) of dimethylbis (2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl) silane and 300 ml of diethyl ether were added to the reaction vessel. It cooled to -70 degreeC with the dry ice-methanol bath. 16 ml (26 mmol) of a 1.59 mol / liter n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 250 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.2 g (13.0 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallization was performed with dichloromethane / hexane, and dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl)- Indenyl}] 1.3 g of hafnium racemate (purity 99% or more) was obtained as yellow-orange crystals (yield 22%).

The resulting proton nuclear magnetic resonance method for racemate identified value according to ^{(1 H-NMR)} are shown below.
_{^{[1 H-NMR (CDCl 3}} ) identification results:
Racemate: δ 0.95 (s, 6H), δ 1.18 (s, 18H), δ 2.09 (s, 6H), δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ6. 75 (dd, 2H), δ 7.09 (d, 2H), δ 7.34 (s, 2H), δ 7.33 (d, 2H), δ 7.35 (d, 4H), δ 7.87 (d, 4H ).

[Synthesis Example 2 of Catalyst Component (A)]
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: (synthesis of component [A-1] (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-exchangeable layered silicate 96% sulfuric acid (1044 g) was added to 3456 g of distilled water in a separable flask, and then montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL: average particle size 19 μm) as a layered silicate. ) 600 g was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, 2400 g of distilled water was added and filtered, and 1230 g of cake-like solid was obtained.
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 whole amount of the cake-like solid was added, and further 522 g of distilled water was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(2-2) Catalyst Preparation and Prepolymerization In a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (65 mL) was added to form a slurry, to which triisobutylaluminum (25 mmol) was added. : 34.6 mL of a heptane solution having a concentration of 143 mg / mL) was added and stirred for 1 hour, then washed to 1/1000 with heptane, and heptane was added so that the total volume became 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 ).

Triisobutylaluminum (0.6 mmol: 0.83 mL of a heptane solution with a concentration of 143 mg / mL) was added to the 1 L flask containing the chemically treated smectite, and then the above solution 1 was added. In addition, the mixture was stirred for 1 hour at room temperature.
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) Production of propylene-based resin (PP-1) After sufficiently replacing the inside of a stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. Hydrogen 7.8NL (0.70 g) and triisobutylaluminum (0.12 mol: 0.47 L of a heptane solution with a concentration of 50 g / L) were added thereto, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst (by weight excluding the prepolymerized polymer) was injected with argon to initiate the polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization. The obtained polymer was dried for 1 hour under a nitrogen stream at 90 ° C. to obtain 18.7 kg of a polymer.
The catalytic activity was 7800 g PP / g catalyst. The MFR was 2.3 g / 10 minutes.

(4) Production of propylene-based resin (PP-2) This was carried out in the same manner as the production of propylene-based resin (PP-1) except that hydrogen to be added was 9.9 NL (0.88 g). Coalescence was obtained. The catalytic activity was 9800 g PP / g catalyst. The MFR was 9.0 g / 10 minutes.

[2] Proprene polymer (B)
Commercially available polypropylene resins (FL203D, FL4, FY4, FY6HA) were used.
(Characteristics of commercial products)
Novatec FL203D (trade name):
Propylene homopolymer manufactured by Nippon Polypro Co., Ltd. (MFR = 3.0 g / 10 min, melting point = 160 ° C.)
Novatec FL4 (trade name):
Propylene homopolymer manufactured by Nippon Polypro Co., Ltd. (MFR = 5.0 g / 10 min, melting point = 162 ° C.)
Novatec FY4 (trade name):
Propylene homopolymer manufactured by Nippon Polypro Co., Ltd. (MFR = 5.0 g / 10 min, melting point = 160 ° C.)
Novatec FY6HA (trade name):
Propylene homopolymer manufactured by Nippon Polypro Co., Ltd. (MFR = 2.4 g / 10 min, melting point = 162 ° C.)

[Example 1]
(1) 100 parts by weight of propylene-based resin (PP-1), 0.05 parts by weight of IRGANOX 1010 (trade name, manufactured by Ciba Specialty Chemicals) as a phenol-based antioxidant, and phosphorus-based antioxidant IRGAFOS168 (trade name, manufactured by Ciba Specialty Chemicals) 0.1 parts by weight, calcium stearate 0.03 parts by weight as a neutralizer, blended with a super mixer, mixed for 3 minutes, extruded A polypropylene resin composition 1 was obtained by melting and kneading with a machine and pelletizing.
Various physical properties measured for the obtained pellets are shown in Table 1.

(2) Production of polypropylene sheet and biaxially stretched sheet-1
The pellet obtained above is put into an extruder having a screw diameter of 65 mm, and the polypropylene sheet obtained by heat melt plasticizing at a resin temperature of 230 ° C. and extruding from a T-shaped die is cooled with water at 60 ° C. It was continuously taken up at a speed of 2 m / min while being cooled and solidified with a mirror-finished metal cast roll and a mirror-finished metal cast cooled with water at 70 ° C., and a width of 800 mm. A sheet having a thickness of 2.0 mm was obtained.
Next, using this sheet, after heating for 6 minutes at 154 ° C. with a biaxial stretching test apparatus (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 4 × 4 simultaneously in the longitudinal and transverse directions at a stretching speed of 1.0 m / min. The film was stretched to double to obtain a biaxially stretched sheet.
This biaxially stretched sheet was evaluated as described above. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the configuration of the present invention was excellent in uniform stretchability.

[Example 2]
Using a polypropylene resin composition obtained by blending 75% by weight of the polypropylene resin composition 1 obtained in Example 1 and 25% by weight of a propylene polymer (B: FL4), the heating temperature of the biaxial stretching apparatus Was carried out in the same manner as in Example 1 except that the temperature was 158 ° C., and a biaxially stretched sheet was obtained.
This biaxially stretched sheet was evaluated as described above. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the configuration of the present invention was excellent in uniform stretchability.

[Example 3]
A biaxially stretched sheet was carried out in the same manner as in Example 1 except that a propylene resin (PP-2) was used instead of the propylene resin (PP-1) and the heating temperature of the biaxial stretching apparatus was 156 ° C. Got.
This biaxially stretched sheet was evaluated as described above. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the configuration of the present invention was excellent in uniform stretchability.

[Comparative Examples 1-2]
Table 1 shows the results of obtaining a biaxially stretched polypropylene sheet in the same manner as in Example 1 at the composition shown in Table 1 and the heating temperature of the biaxial stretching apparatus.
A biaxially stretched polypropylene sheet that does not satisfy the constitution of the present invention is inferior in uniform stretchability and cannot be used as a thermoforming sheet.

[Example 4]
(3) Production of polypropylene sheet and biaxially oriented sheet-2
The pellet obtained in Example 1 was put into an extruder having a screw diameter of 65 mm, and a polypropylene sheet obtained by heating and plasticizing at a resin temperature of 230 ° C. and extruding from a T-shaped die was internally filled with 80 ° C. water. It is continuously picked up at a speed of 1.0 m / min while being cooled and solidified by sandwiching it between a cooled metal cast roll with a mirror finish and a mirror finish metal cast cooled with water at 90 ° C. A sheet having a width of 700 mm and a thickness of 3.0 mm was obtained.
Then, using this sheet, after heating at 155 ° C. for 3 minutes with a biaxial stretching test apparatus (Brookner KAROIV), simultaneously up to 3 × 3 times in the longitudinal and transverse directions at a stretching speed of 1.0 m / min. Stretched to obtain a biaxially stretched sheet.
This biaxially stretched sheet was evaluated as described above. The results are shown in Table 2.
The biaxially stretched polypropylene sheet satisfying the configuration of the present invention was excellent in uniform stretchability.

[Examples 5 to 11]
A biaxially oriented polypropylene sheet was obtained in the same manner as in Example 4 at the composition shown in Table 2 and the heating temperature of the biaxially oriented machine. The results are shown in Table 2.
These biaxially stretched sheets were evaluated as described above. The results are shown in Table 2.
The biaxially stretched polypropylene sheet satisfying the configuration of the present invention was excellent in uniform stretchability.

[Comparative Example 3]
A biaxially oriented polypropylene sheet was obtained in the same manner as in Example 4 at the composition shown in Table 2 and the heating temperature of the biaxially oriented machine. The results are shown in Table 2.
A biaxially stretched polypropylene sheet that does not satisfy the constitution of the present invention is inferior in uniform stretchability and cannot be used as a thermoforming sheet.

  The biaxially stretched sheet of the present invention is excellent in uniform stretchability at a low magnification, and can be suitably used as a material for thermoformed products.

Claims (9)

Propylene polymer (A) 100 to 5% by weight characterized by satisfying the requirements defined in the following (i) to (vi), and a propylene polymer having a melting point of 150 to 170 ° C. measured by DSC ( A biaxially stretched polypropylene sheet obtained by stretching an extruded sheet made of a polypropylene resin composition containing 0 to 95% by weight of B) in a biaxial direction.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 g / 10 min or more and 20 g / 10 min or less.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
(Iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more. The biaxially oriented polypropylene sheet according to claim 1, wherein the propylene polymer (A) further satisfies the following requirements (vii) and (viii).
(Vii) (MT230 ° C.) ≧ 5 g
[In the formula, MT230 ° C. is measured using a melt tension tester, capillary: diameter 2.1 mm, cylinder diameter: 9.6 mm, cylinder extrusion speed: 10 mm / min, winding speed: 4.0 m / min, temperature: 230 It represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [where, MaxDraw (maximum winding speed) is the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. Represent. ] The biaxially oriented polypropylene sheet according to claim 1 or 2, wherein the propylene polymer (A) further satisfies the following requirement (ix).
(Ix) (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 biaxially stretched polypropylene sheet according to any one of claims 1 to 3, wherein the propylene polymer (A) further satisfies the following requirement (x).
(X) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position that is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0.   The biaxially stretched polypropylene sheet according to any one of claims 1 to 4, wherein the biaxially stretched polypropylene sheet is stretched 1.5 times or more in each of MD and TD, and stretched 3 to 30 times at a surface magnification. 6. The composition according to claim 1, wherein 0.1 to 1 part by mass of a nucleating agent represented by the following general formula (1) is blended with respect to 100 parts by mass of the polypropylene resin composition. 2. A biaxially oriented polypropylene sheet according to 1.

[In the formula, n is an integer of 0 to 2, and R1 to R5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, a carbonyl group, a halogen group or a phenyl group, and R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]   The biaxially stretched polypropylene sheet according to any one of claims 1 to 6, wherein the sheet thickness after stretching is 0.1 mm to 1 mm.   The biaxially stretched polypropylene sheet according to any one of claims 1 to 7, wherein a standard deviation of the sheet thickness after stretching is 50 or less.   The molded object obtained by thermoforming the biaxially-stretched polypropylene sheet of any one of Claims 1-8.

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