JP6787070B2 - Biaxially stretched polypropylene sheet - Google Patents

Description

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

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

However, the propylene-based polymer has a drawback that its transparency is significantly inferior to that of 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 copolymerizing propylene and α-olefin to lower the crystallinity and improve the transparency is used. In the method of improving transparency by copolymerizing propylene and α-olefin, the transparency is improved as the amount of α-olefin is increased, but the rigidity of the product is significantly reduced, so only a small amount of α-olefin is used. There is a problem that it cannot be done and the transparency improvement effect is naturally limited.

Therefore, a method of improving transparency by adding a nucleating agent such as dibenzylidene sorbitol, an organic carboxylic acid, a metal salt of an organic carboxylic acid, or a metal phosphate of an organic phosphate to a propylene-based polymer is generally used. .. In particular, dibenzylideneacetone sorbitol-based nucleating agent is the most effective and is widely used as a packaging product for foods, daily necessities, etc. (see Patent Document 1).

Japanese Unexamined Patent Publication No. 4-339847

On the other hand, thermoforming methods such as vacuum forming, vacuum pressure air forming, and solid phase pressure air forming, in which a thermoplastic resin is extruded into a sheet and then the sheet is reheated to obtain a desired product, are easy to mold and productive. Because of its high price, it is suitable for mass production and it is easy to obtain multi-layered products, so it is widely used.

However, since polypropylene is a crystalline resin, compared to polystyrene and polyethylene terephthalate, in the case of thermoforming methods such as vacuum forming and vacuum forming using an extruded sheet, the sheet is reheated to obtain a product. It is difficult to obtain transparency and it is difficult to mold a product that is valuable as a product.
As described above, there is a demand for a thermoformed packaged product having both transparency and rigidity by 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 in low magnification stretching, and a molded product obtained by thermoforming the biaxially stretched polypropylene sheet.

The present inventor has conducted diligent research in order to solve the above problems. It is known that polypropylene sheets have improved physical properties such as rigidity and transparency by biaxial stretching.
Generally, polypropylene, which is a crystalline resin, has a yield point, and when it is stretched at a low magnification, necking occurs and uneven stretching (uneven thickness) occurs. The stretching ratio of the sequentially biaxially stretched polypropylene known as OPP is usually performed at a high magnification of about 5 × 10 times in length × width = 5 × 10 times, but the target stretched sheet (thickness 0.1 to 1 mm) is obtained by high magnification stretching. ) Is impossible due to the thickness of the original fabric.

As a result of studying a polypropylene resin in which stretching unevenness is unlikely to occur in low-magnification stretching, the present inventor comprises a biaxially stretched sheet using a specific propylene-based polymer and a resin composition containing the propylene-based polymer. We have found that the biaxially stretched sheet is less likely to cause uneven thickness 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, 100 to 5% by weight of the propylene-based polymer (A), which is characterized by satisfying the requirements specified in (i) to (vi) below, has a melting point measured by DSC. Provided is a biaxially stretched polypropylene sheet obtained by biaxially stretching an extruded sheet made of a polypropylene-based resin composition containing 0 to 95% by weight of a propylene-based polymer (B) at 150 to 170 ° C. ..
(I) The melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 g / 10 minutes or more and 20 g / 10 minutes or less.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) to 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 components 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 the temperature elution separation (TREF) by orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or lower is 3.0% by weight or less.
(V) ^{13 The} isotactic triad fraction (mm) measured by C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of extensional viscosity is 6.0 or more.

Further, according to the second invention of the present invention, in the first invention, the propylene-based polymer (A) further satisfies the following requirements (vii) and (viii). Sheets are provided.
(Vii) (MT230 ° C) ≧ 5 g
[In the formula, MT230 ° C. uses 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. Represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [In the formula, 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. ]

Further, according to the third invention of the present invention, in the first or second invention, the propylene-based polymer (A) is further characterized in that the biaxially stretched polypropylene sheet 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 length of 8.00 mm and a diameter of 1.00 mmφ, sets the temperature inside 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 rapidly cooled in ethanol, and the strand diameter of the extruded product at that time is divided by the orifice diameter. ]
Further, according to the fourth invention of the present invention, in any one of the first to third inventions, the propylene-based polymer (A) is further biaxially stretched, characterized in that it 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 50% higher than the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp). On the lower molecular weight side, H ₅₀ is on the higher molecular weight side than Tp), and when α and β are defined as α = H ₅₀ -Tp and β = Tp-L ₅₀ , α / β is larger than 0.9 and 2 It is less than 0.0.

Further, 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 the surface magnification is 3 to 30 times. A biaxially stretched polypropylene sheet formed 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。 Further, according to the sixth invention of the present invention, in any one of the first to fifth inventions, nucleation represented by the following general formula (1) is formed with respect to 100 parts by mass of the polypropylene-based resin composition. Provided is a biaxially stretched polypropylene sheet, which comprises 0.1 to 1 part by mass of an agent.

[However, in the formula, n is an integer of 0 to 2, and R1 to R5 are the same or different, and are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms and alkoxy groups having 2 to 20 carbon atoms, respectively. , 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.

Further, according to the seventh aspect of the present invention, there is provided a biaxially stretched polypropylene sheet according to any one of the first to sixth inventions, wherein the sheet thickness after stretching is 0.1 mm to 1 mm.

Further, according to the eighth invention of the present invention, there is provided a biaxially stretched polypropylene sheet according to any one of the first to seventh inventions, wherein the standard deviation of the sheet thickness after stretching is 50 or less.

Further, according to the ninth invention of the present invention, there is provided a molded product obtained by thermoforming the biaxially stretched polypropylene sheet according to any one of the first to eighth inventions.

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

It is a figure which shows an example of the molecular weight distribution curve in GPC of the propylene-based polymer (A) which concerns on this invention. It is a figure of the explanation of the baseline and the section of the chromatogram in GPC. It is a figure which shows an example of the molecular weight distribution derived from [A-1] and [A-2] in GPC of the propylene-based polymer (A) according to the present invention. It is a plot figure which shows an example of the extensional viscosity measured by the uniaxial extensional viscometer. It is a figure explaining the correlation of ME (memory effect) and MFR of the propylene-based polymer (A) which concerns on this invention.

The biaxially stretched polypropylene sheet of the present invention comprises the following (i) to (vi), or in addition to them, (vii) and (viii), or in addition to them, (ix) and / or (x). 100 to 5% by weight of the propylene-based polymer (A) having the characteristics and properties of the above, and 0 to 95% by weight of the propylene-based polymer (B) having a melting point of 150 to 170 ° C. measured by DSC. A biaxially stretched polypropylene sheet made of a resin composition.
In addition, 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 ( 100 to 5% by weight of the propylene-based polymer (A) having the characteristics and properties of x) and 0 to 95% by weight of the propylene-based polymer (B) having a melting point of 150 to 170 ° C. measured by DSC were blended. It is obtained by stretching an extruded sheet made of a propylene-based resin composition in the biaxial direction.
(I) The melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 to 20 g / 10 minutes.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) to 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 components 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 the temperature elution separation (TREF) by orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or lower is 3.0% by weight or less.
(V) ^{13 The} isotactic triad fraction (mm) measured by C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of extensional viscosity is 6.0 or more.
(Vii) (MT230 ° C) ≧ 5 g
[In the formula, MT230 ° C. uses 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. Represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [In the formula, 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 length of 8.00 mm and a diameter of 1.00 mmφ, sets the temperature inside 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 rapidly cooled in ethanol, and the strand diameter of the extruded product at that time 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 50% higher than the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp). On the lower molecular weight side, H ₅₀ is on the higher molecular weight side than Tp), and when α and β are defined as α = H ₅₀ -Tp and β = Tp-L ₅₀ , α / β is larger than 0.9 and 2 It is less than 0.0.

Hereinafter, the constituent 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 1. Propylene polymer (A)
The propylene-based polymer (A) constituting the propylene-based resin composition used in the biaxially stretched polypropylene sheet of the present invention includes the above (i) to (vi), or in addition to them, (vii) and (viii). ), Or in addition to them, it has the characteristics / properties of (ix) and / or (x).
Hereinafter, each item will be described in sequence.

(1) Definition and identification method of structure and long-chain branched structure of propylene-based polymer (A) The propylene-based polymer (A) according to the present invention has physical properties and melt processability in which melt fluidity and melt tension are controlled. It is a long-chain branched propylene-based polymer with an excellent balance of.
It is considered that the propylene-based polymer (A) according to the present invention has significantly improved melt properties due to the introduction of the long-chain branching.
Generally, ¹³ C-NMR is used for detecting and quantifying the branch structure and the number of branches. Further, ¹³ C-NMR, GPC-vis, and GPC-malls are used for detecting and quantifying the number of branches and the distribution of branches.
Regarding the branching structure, the present inventor infers as follows in consideration of the mechanism and mechanism 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, a special chain transfer reaction generally called β-methyl elimination causes the polymer piece terminal to have a propenyl structure mainly. Shown, so-called macromers are generated.
The propenyl structure at the terminal stopped by the β-methyl elimination reaction is shown below (Reference: Macromol. Rapid Commun. 2000, 21, 1103-1107).

It is speculated that this macromer is incorporated into an active species derived from the catalyst component [A-2], which can generate a higher molecular weight and has better copolymerizability, and the macromer copolymerization is proceeding.
Therefore, the propylene-based polymer (A) according to the present invention has a specific branched structure as shown in the following structural formula (2).
In the structural formula (2), Ca, Cb, and Cc indicate methylene carbon adjacent to the branched carbon, Cbr indicates the methine carbon at the root of the branched chain, and P ¹ , P ² , and P ³ are propylene-based weights. Shows coalesced residues.
P ^{1, P} 2, ^{P 3} is in itself, and is Cbr described in structural formula (2), may also contain another branch carbon (Cbr).

Such a branched structure is identified by ¹³ C-NMR analysis. The attribution of each peak is described in Macromolecules, Vol. 35, No. 10. The description on pages 3839-3842, 2002 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) were observed at 44.0 to 44.1 ppm, 44.7 to 44.8 ppm, and 44.8 to 44.9 ppm, respectively, 31.6. Methine carbon (Cbr) is observed at ~ 31.7 ppm. The methine carbon observed at 31.6 to 31.7 ppm may be abbreviated as branched carbon (Cbr) below.
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 indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer. It can be distinguished from the branch having 4 or less carbon atoms by the difference in the peak position of the branched carbon (see Macromol. Chem. Phys. 2003, Vol. 204, p. 1738).

In general, considering the regulation of the number and length of branches of a polymer, the larger the number of branches, the better the melt property. On the other hand, if the number of branches is unevenly distributed among the molecules, gel is generated, and it is considered that the effect of improving the melt property is also reduced.
The number of branches is defined as the number of branches (density) per 1000 total skeleton-forming carbons of branched carbon (Cbr) observed at 31.6 to 31.7 ppm by utilizing the above attribution by ¹³ C-NMR. .. However, the total skeleton-forming carbon means all carbon atoms other than methyl carbon.

From a rheological point of view, it is considered necessary that the propylene-based polymer (A) exhibiting improved melt properties according to the present invention has a number of branches of 0.01 or more.
Further, if the amount of branching is too large, there is a concern that gel will be formed and the appearance of the molded product will be spoiled. Further, 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, which is a so-called deterioration of melt ductility.
Therefore, the number of branches is preferably 0.4 or less, preferably 0.2 or less, and more preferably less than 0.1.
Even when ¹³ C-NMR of the current high magnetic field NMR is used, the measurement limit is 0.1 or more, and the quantification has not been reached so far. If the branch itself is detected, it is evaluated as "trace".

Further, the propylene-based polymer (A) according to the present invention is required to have a branch length of 7,000 or more, which is an entangled molecular weight of polypropylene. When converted to the number of skeletal carbons, it corresponds to about 400 or more. The skeletal carbon here means all carbon atoms other than methyl carbon. It is considered that the longer the branch length, the better the melt property.
Therefore, the branched chain length of the propylene-based polymer (A) according to the present invention is 500 (polypropylene molecular weight conversion: 11,000) or more, preferably 1000 skeleton carbon numbers (polypropylene molecular weight conversion: 2. It is 10,000) or more, and more preferably 2000 carbon atoms (polypropylene molecular weight conversion: 42,000) or more.
Strictly speaking, the polypropylene molecular weight conversion value referred to here is different from the molecular weight value measured by GPC, but is close to 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 the number average molecular weight (Mn) measured by GPC. It will be replaced with more than 10,000.

In addition, when considering the polymerization mechanism, macromers generated from the active species derived from the catalyst component [A-1] are incorporated into the main chain to form a branched structure, so that the average molecular weight of the macromers is the incorporated branched chain. Characterized as average molecular weight.
For example, in the propylene-based polymer (A) according to the present invention, when the molecular weight of macromer produced from the active species derived from [A-1] is 50,000 in terms of number average molecular weight, the average molecular weight of the incorporated branched chain is There are 50,000, which is interpreted as 2400 when converted to skeletal carbon.
The number average molecular weight of the macromer produced from the active species derived from [A-1] is based on the peak top of the portion derived from [A-1] in GPC or the molecular weight when [A-1] is polymerized alone. Can be estimated.

On the other hand, the branched distribution of the polymer can be measured by GPC-vis or GPC-malls, but from the viewpoint of the polymerization mechanism, the macromer derived from [A-1] has a higher molecular weight and higher copolymerizability. Since it is considered that the branch is generated by being incorporated into the active species derived from the component [A-2], it is considered that the long-chain branch is introduced into the molecular weight component 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 branch distribution has a high molecular weight side ([A-2] -derived side). Also, it is considered that the distribution form has a branch introduced.
Further, in the molecular weight component derived from [A-1], there is also a branched structure formed by incorporating macromer by [A-1] itself.
An example of the molecular weight distribution derived from [A-1] and [A-2] is shown in FIG.

Explaining the relationship between the number of branches and the distribution of branches, it is generally considered necessary to have a large number of branches in order to improve the melt properties. According to JP-A-2007-154121, the number of branches is 0.1 / Propylene homopolymers with 1000 skeleton carbons or more are disclosed.
However, the strain hardening degree in the measurement of the extensional viscosity is less than 6, and it is improved even when the strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (A) according to the present invention is 6.0 or more. The effect is not enough. This is because the desired branching component is not sufficiently introduced because it is produced by a single complex, and it means that the effect of improving the melt property 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 combining a plurality of complexes and introducing branches on the high molecular weight side, the melt properties can be improved. It is a remarkable improvement.

Further, when the stereoregularity of the side chain is explained, 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 will be reduced. Therefore, in order to obtain a polymer having higher rigidity, it is preferable that both the side chain and the main chain have high stereoregularity. The value is 95% or more in mm fraction for both the main chain and the side chain. It is particularly preferably 96% or more, and further preferably 97% or more.
The stereoregularity of the side chain is considered to be equal to the stereoregularity of the polymer by [A-1] alone.

(2) Physical Properties of Propylene Polymer (A) The propylene polymer (A) in the present invention has an excellent balance between physical properties and melt processability in which melt fluidity and melt tension are controlled. The physical properties of the propylene-based polymer (A) will be described.

(2-1) Melt flow rate (MFR):
The propylene-based polymer (A) according to the present invention requires that the melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 kg is 0.5 to 20 g / 10 minutes.
The melt flow rate (MFR) of the propylene-based 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 raw material is excellent.
The melt flow rate (MFR) is a test condition in accordance with JIS K6921-2 "Plastic-Polypropylene (PP) molding and extrusion materials-Part 2: How to make test pieces and how to determine their 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 ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC) and Mw / Mn (Q value). It needs to be in the range of 5 to 10.5.
The Q value is an index showing the spread of the molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is. If the Q value is too small, the distribution is narrow and the balance between melt fluidity and workability becomes poor. Therefore, 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 it is not possible to obtain satisfactory physical properties. 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 the spread of the molecular weight distribution obtained from the molecular weight distribution curve by GPC toward the high molecular weight side:
In the propylene-based polymer (A) according to the present invention, 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 50% higher than the peak height is used. When L ₅₀ and H ₅₀ (L ₅₀ is on the low molecular weight side of Tp and H ₅₀ is on the high molecular weight side of Tp) and α and β are defined as α = H ₅₀ -Tp and β = Tp-L ₅₀ , respectively, α It is desirable that / β is greater than 0.9 and less than 2.0. Here, α / β is an index showing the bias of the spread of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is shown by the molecular weight distribution curve obtained by GPC. That is, a graph is created in which the common logarithm of the molecular weight (MW) is used as the horizontal axis and the relative differential mass of the molecule corresponding to the MW is plotted on the vertical axis.
The molecular weight (MW) referred to here is the molecular weight of each molecule 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 can be obtained from the created graph. In the present invention, as described above, it is desirable that α / β is larger 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 α / β of this most probable distribution is calculated to be 0.9.
Therefore, it means that the molecular weight distribution of the propylene homopolymer of the present invention is further spread to the higher molecular weight side as compared with the molecular weight distribution of the polymer uniformly polymerized at a single active point.
The propylene-based polymer (A) according to the present invention preferably has α / β of more than 0.9, preferably 1.0 or more, and more preferably 1.1 or more. Since α / β is larger than 0.9 and the amount of high molecular weight component is relatively sufficient, the melt tension and the swell ratio are high, and the moldability is good.
Further, the propylene-based polymer (A) according to the present invention preferably has an α / β of less than 2.0, preferably less than 1.7, and more preferably less than 1.6. When α / β is less than 2.0, the amount of the high molecular weight component does not become too large, and the fluidity is good.
Two or more peaks may appear in the molecular weight distribution curve. In that case, the maximum peak can be replaced with the peak of the present invention. When two or more H _50s appear, they can be replaced with the molecular weight on the highest molecular weight side. Similarly, when two or more L _50s appear, they can be replaced with the molecular weight on the lowest molecular weight side.

(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 (sometimes abbreviated as 2 million or more)) is 0.4% by weight or more and less than 10% by weight.
The ratio of 2 million or more (W (2 million or more)) is an index showing the ratio of extremely high molecular weight components contained in the polymer.
W (2 million or more), which is the ratio of the extremely high molecular weight components, has a molecular weight (M) of 2 million (Log (M) = 6) in the integrated molecular weight distribution curve (total amount is standardized to 1) obtained by GPC. .3) The integrated values up to the following are defined as values subtracted from 1. An example of the integrated molecular weight distribution curve is also shown in FIG.

The propylene-based polymer (A) according to the present invention preferably has a W (2 million or more) of 0.4% by weight or more, preferably 1.0% by weight or more, and more preferably 2 It is 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, particularly a component having a very high molecular weight is contained, the melt tension and the swell ratio are high, and the moldability is good. Become. It is considered that this component having a very high molecular weight contains a branched component as described above.
Further, the propylene-based polymer (A) according to the present invention preferably has a W (2 million or more) of less than 10% by weight, preferably less than 6.0% by weight, and 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 gel due to the component having a very high molecular weight is suppressed, and the appearance of the molded product is also good. Further, when W (2 million or more) is less than 10% by weight, it is possible to prevent the so-called deterioration of melt ductility, in which the melt breaks when stretched at high speed during molding.

The weight average molecular weight (Mw), Q value, α / β, and W (2 million or more) values defined above are all obtained by gel permeation chromatography (GPC). The details of the measuring method and measuring device are as follows.

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

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving the sample at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are as shown in FIG.
Further, the conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve using standard polystyrene prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximating with the least squares method is used.
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 Elution Separation (TREF) by Orthodichlorobenzene (ODCB):
The propylene-based polymer (A) according to the present invention needs to have an elution curve of 3.0% by weight or less at a temperature of 40 ° C. or lower in the elution curve obtained by temperature-temperature elution fractionation (TREF) measurement. It is preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and very preferably 0.5% by weight or less. When the amount of the component eluted at a temperature of 40 ° C. or lower is 3.0% by weight or less, the machine such as the decrease in crystallinity of the entire product and the rigidity of the product due to the low crystallinity component eluted at a temperature of 40 ° C. or lower. It is possible to suppress a decrease in target strength.

The details of the method for measuring the elution component by the temperature-temperature elution separation (TREF) are as follows.
The sample is dissolved in orthodichlorobenzene at 140 ° C. to prepare a solution. After introducing this into a TREF column at 140 ° C., the mixture is cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, subsequently cooled to 40 ° C. at a temperature lowering rate of 4 ° C./min, and then held for 10 minutes. Then, the solvent ortodichlorobenzene was flowed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at 40 ° C. were eluted in the TREF column for 10 minutes, and then the heating rate was 100 ° C./hour. The column is linearly heated to 140 ° C. to obtain an elution curve.

Column size: 4.3 mm φ x 150 mm
Column filler: 100 μm surface-inactivated glass beads Solvent: Ortodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength infrared detector, FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

(2-6) ¹³ Isotactic triad fraction (mm) measured by C-NMR:
The propylene-based polymer (A) according to the present invention has a stereoregularity in which the mm fraction of the propylene unit 3-chain obtained by ¹³ C-NMR is 95% or more.
The mm fraction is the ratio of the propylene unit 3 chain in which the direction of the methyl branch in each propylene unit is the same in any propylene unit 3 chain consisting of a head-tail bond in the polymer chain. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is isotactically controlled, and the higher the value, the higher the control.
If the mm fraction is smaller than this value, the mechanical properties such as the elastic modulus of the product will decrease. Therefore, the mm fraction is preferably 96% or more, and more preferably 97% or more.
The stereoregularity of the main chain and the side chains is determined by the stereoregular ability of the catalyst components [A-1] and [A-2] used in the method for producing the propylene-based polymer (A) described later. If the stereoregularity of the side chain is low, the crystallinity of the entire main chain will be reduced even if the crystallinity of the main chain is high. Therefore, in order to obtain a polymer having higher rigidity, it is preferable that both the side chain and the main chain have high stereoregularity. The value is 95% or more in mm fraction for both the main chain and the side chain. It is particularly preferably 96% or more, and further preferably 97% or more.

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

The mm fraction is measured using the ¹³ C-NMR spectrum measured under the above conditions.
Spectrum attribution was made with reference to Macromolecules, (1975), 8 squares, p. 687, and Polymer, Vol. 30, p. 1350 (1989).

A more specific method for determining the mm fraction will be described below.
Peaks derived from the methyl group of the central propylene of the three chains head-to-tail bonded around the propylene unit occur in three regions depending on the configuration.
mm: Approximately 24.3 to approximately 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 shifts slightly depending on the molecular weight and the copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structures.

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

Further, the propylene-based polymer (A) according to the present invention may have the following partial structure containing ethylene units.

The methyl group (PPE-methyl group) of the central propylene unit of the partial structure PPE resonates in the mr region near 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 it resonates in the nearby rr region, when having such a partial structure, it is necessary to reduce the peak area based on the PPE-methyl group and the EPE-methyl group from the peak area 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 (resonating around 31.0 ppm), and the peak area based on the EPE-methyl group resonates around the corresponding methine group (resonating around 33.3 ppm). ) Can be evaluated by the peak area.

Further, the partial structure including the irregularly positioned unit may have the following structure (i), structure (ii), structure (iii) and structure (iv).

Of these, carbon A, A'and A'peaks appear in the mr region, carbon B and B'peaks appear in the rr region, and carbon C and C'peaks appear in 16.8 to 17.8 ppm. ..
Therefore, when calculating the mm fraction in the formula (I), the carbon that appears in the mr and rr regions at peaks that are not based on the head-tail bonded three-chain from the peak area of the mr region and the peak area of the rr region, respectively. It is necessary to reduce the peak area based on A, A', A ", B, B'.

The peak area based on carbon A is carbon D (resonance near 42.4 ppm), carbon E and G (resonance near 36.0 ppm) and carbon F (38.7 ppm) of the irregular partial structure [structure (i)]. It can be evaluated from 1/4 of the sum of the peak areas of (resonance in the vicinity).
The peak area based on carbon A'is carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J (34.1 ppm) of the position irregular partial structure [structure (ii) and structure (iii)]. It can be evaluated by the sum of 2/5 of the sum of the peak areas of carbon K (resonance in the vicinity) and the peak area of carbon K (resonance in the vicinity of 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. Moreover, the peak area based on carbon B'can be evaluated by carbon K.
The positions of the carbon C peak and the carbon C'peak do not need to be considered because they are not related to the mm, mr, and rr regions of interest.
From the above, since the peak areas of mm, mr and rr can be evaluated, the mm fraction of the three-chain portion consisting of the head-tail bond centered on the propylene unit can be obtained according to the above formula (I).

(2-7) Strain hardening degree (λmax) in measuring extensional viscosity:
The propylene-based polymer (A) according to the present invention needs to have a strain hardening degree (λmax) of 6.0 or more in the measurement of extensional viscosity.
The strain hardening degree (λmax) is an index showing the strength at the time of melting, and when this value is large, there is an effect that the melting tension is improved. Therefore, the strain hardening degree needs to be 6.0 or more, preferably 10.0 or more, and more preferably 15.0 or more.
Further, this strain hardening degree is an index showing the non-linearity of extensional viscosity, and it is usually said that the more the molecules are entangled, the larger this value becomes. The entanglement of molecules is affected by the amount of branching and the length of the branched chain. Therefore, the longer the amount of branching and the length of branching, the greater the strain hardening degree.

Generally, in order to exhibit a high degree of strain hardening, the length of the branch is required to be 7,000 or more, which is the entangled molecular weight of polypropylene. When converted to the number of skeletal carbons, it corresponds to about 400 or more. The skeletal carbon here means all carbon atoms other than methyl carbon. It is considered that the longer the branch length, the better the melt property. It is believed that strain hardening can be detected even in the slower strain rate region in the measurement of extensional viscosity, especially when a longer branched chain is introduced.
Therefore, as described above, the branched chain length of the propylene-based polymer (A) according to the present invention is 500 skeletal carbon atoms (polypropylene molecular weight conversion: 11,000) or more, and preferably 1000 skeletal carbon atoms (polypropylene molecular weight). Conversion: 21,000) or more, more preferably skeleton carbon number 2000 (polypropylene molecular weight conversion: 42,000) or more.
As described above, the polypropylene molecular weight conversion value referred to here is strictly different from the molecular weight value measured by GPC, but is close to 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, and 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 degree of strain hardening, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, details of the measuring method and the measuring device are described in the publicly known document Polymer 42. (2001) Although there is a method described in 8663, the following can be mentioned as preferable measuring methods and measuring instruments.

Measurement method 1:
Equipment: Ares manufactured by Rheometrics
Jig: Industrial Viscosity Fixture manufactured by TA Instruments Co., Ltd.
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: Press-mold to prepare a sheet having a size of 18 mm × 10 mm and a thickness of 0.7 mm.

Measurement method 2:
Equipment: Melten Rheometer, manufactured by Toyo Seiki Seisakusho Co., Ltd.
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: Using a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd., an extrusion 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.

Calculation method:
Strain rate: The extensional viscosity at 0.1 / sec is plotted on a log-log graph with time t (seconds) on the horizontal axis and extensional viscosity ηE (Pa · seconds) on the vertical axis. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the strain amount reaches 4.0 is obtained, and on the approximate straight line up to that time. Let the viscosity of be ηlin.
FIG. 4 is an example of a plot of extensional 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 changes depending on the difference in strain rate. It is considered that the strain rate dependence of the strain hardening degree changes 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, it is desirable that the memory effect (ME) 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 length of 8.00 mm and a diameter of 1.00 mmφ, sets the temperature inside 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 rapidly cooled in ethanol, and the strand diameter of the extruded product at that time is divided by the orifice diameter. ]

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

As shown in FIG. 5, the propylene-based polymer (A) according to the present invention has a large ME in terms of MFR as compared with a conventionally known polymer 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)

As a measurement method of the memory effect (ME), a melt indexer manufactured by Takara Co., Ltd. is used, and a load is applied to extrude the orifice diameter of 1.0 mm and the length of 8.0 mm at 190 ° C., and the extrusion speed is 0.1 g. The load is adjusted to / minute, 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 ductility:
Since the propylene-based polymer (A) according to the present invention has a controlled branch structure (branch amount, branch length, branch distribution), the melt properties are remarkably improved. That is, it has excellent melt fluidity while having high melt tension. As an index of the melt tension and the melt fluidity, it can be expressed by the balance between the melt tension (MT) and the maximum take-up speed (MaxDraw) measured by the following measuring methods.

A method for measuring the melt tension (MT) and the maximum take-up speed (MaxDraw) will be described.
Using Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., the tension detected by the pulley when the resin is extruded into a string shape and wound on a roller is defined as the melt tension (MT) under the following conditions.
Capillary: 2.1 mm in diameter
Cylinder diameter: 9.6 mm
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 object is cut is defined as the maximum winding speed (MaxDraw). To do.
Here, the larger the MT value, the higher the melt tension, and the larger the MaxDraw, the better the fluidity and ductility.
In the propylene-based polymer of the present invention, the melt tension is improved by expanding the molecular weight distribution and introducing branching. Therefore, the MT is preferably 5 g or more, more preferably 10 g or more, still more preferably 15 g. That is all.

Further, as described above, the MT value can be increased by increasing the high molecular weight component or the number of branches, 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 the string-like material to break, and the MaxDraw does not increase. That is, the melt ductility deteriorates.
By controlling the branching component, the propylene-based polymer (A) according to the present invention can have a large MaxDraw while maintaining a high MT, and the balance between melt tension and melt ductility is improved.
Therefore, in the propylene-based polymer (A) according to the present invention, MaxDraw is preferably 10 m / min or more, more preferably 20 m / min or more, and further preferably 30 m / min or more.

(3) Method for Producing Propylene-based Polymer (A) The method for producing the propylene-based polymer (A) according to the present invention has a balance between physical properties and processability in which the above-mentioned melt fluidity and melt tension are controlled. Any method may be used as long as an excellent long-chain branched propylene polymer can be obtained, and there is no particular limitation. For example, as a method for introducing a controlled branched component, a method using a plurality of complexes as described below can be mentioned. be able to.

That is, it is a method for producing the above-mentioned long-chain branched propylene-based polymer, and is characterized in that the following catalyst components (A), (B) and (C) are used as the propylene polymerization catalyst. Examples thereof include a method for producing a polymer.
(A): At least one kind from the component [A-1] which is a compound represented by the following general formula (1), and at least one from the component [A-2] which is a compound represented by the general formula (2). Type, 2 or more selected transition metal compounds of 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-exchangeable layered silicate (C): Organoaluminium compound

Hereinafter, the catalyst components (A), (B) and (C) will be described in detail.
(B) Catalyst component (A)
(I) Component [A-1]: Compound represented by the general formula (3)

[In the 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. Further, R ¹³ and R ¹⁴ may each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or a plurality of heteroelements selected from these aryls having 6 to 16 carbon atoms. Represents a group, a heterocyclic group containing nitrogen, oxygen or sulfur having 6 to 16 carbon atoms. Further, X ¹¹ and Y ¹¹ independently have 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, and a halogenation having 1 to 20 carbon atoms. hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, Represents a silylene group or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

Heterocyclic groups containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² are preferably 2-frill groups, substituted 2-furyl groups, substituted 2-thienyl groups, substituted. It is a 2-furfuryl group, more preferably a substituted 2-furyl group.
Further, as the substituent of the substituted 2-furyl group, the substituted 2-thienyl group and the substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group can be used. 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.
In addition, R ¹¹ and R ¹² are particularly preferably 2- (5-methyl) -frill groups. Further, it is preferable that R ¹¹ and R ¹² are the same as each other.

Carbon is an aryl group having 6 to 16 carbon atoms of R ¹³ and R ¹⁴ and which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. In the range of the number 6 to 16, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms are contained on the aryl cyclic skeleton. It may have a hydrocarbon group as a substituent.
As R ¹³ and R ¹⁴ , preferably at least one is a phenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl. It is a group, a chlorophenyl group, a naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-t-butylphenyl group, or a 4-chlorophenyl group. Further, when two R ₂ are identical to each other is preferable.

In the general formula (3), X ¹¹ and Y ¹¹ are co-ligands and react with the co-catalyst of the component (B) to produce an active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently hydrogen, halogen groups, and hydrocarbon groups having 1 to 20 carbon atoms. Indicates 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. ..

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 Indicates either a group or a gelmilene group. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ^11, methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, alkylene group and the like; arylalkylene group such as diphenylmethylene; silylene group; methylsilylene, dimethylsilylene, diethyl silylene, di Alkyl silylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; Alkyloligosilylene group such as tetramethyldisyrylene; Germilene group; Alkylgermilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germilene group; aryl gelmilene group and the like can be mentioned. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.

Among the compounds represented by the general formula (3), the 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'-dimethylgermilenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgelmilenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2-( 5-t-Butyl-2-furyl) -4-phenyl-indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (4,4) 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-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) {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' − The Methylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-) 2-Frill) -4- (4-t-Butylphenyl) -Indenyl}] Hafnium, Dichloro [1,1'-dimethylsilylenebis {2- (2-Frill) -4- (1-naphthyl) -Indenyl} ] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2) -Frill) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthrill) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5) -Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] 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-Frill) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl 2--2-furyl) -4- (2-phenanthrill) ) -Indenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl2-frill) -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 Nil}] Hafnium, etc. can be mentioned.

Of these, more preferred are dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylgel. Millenbis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloromethane [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-( 4-Chlorophenyl) -indenyl}] hafnium, dichloromethane [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-naphthyl-indenyl}] hafnium, dichloromethane [1,1'-dimethyl Dichloromethane {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

Particularly preferred are 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, dichloromethane [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 the general formula (4), R ²¹ and R ²² are independently hydrocarbon groups having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are independent of halogen, silicon, oxygen, and so on. It is an aryl group having 6 to 16 carbon atoms which may contain sulfur, nitrogen, boron, phosphorus or a plurality of hetero elements selected from these. X ²¹ and Y ²¹ independently have 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, and a halogenated hydrocarbon having 1 to 20 carbon atoms. group, an oxygen-containing hydrocarbon group, an amino group or nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon atoms Represents a silylene or gelmilene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

Each of R ²¹ and R ²² is 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 the like, with preference given to methyl. , Ethyl, n-propyl.
Further, each of the above R ²³ and R ²⁴ independently contains a halogen, silicon, or a plurality of heteroelements selected from these, which have 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms. Is also a good aryl group. Preferred examples are 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 Examples thereof include −dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like.

Further, X ²¹ and Y ²¹ are co-ligands and react with the co-catalyst of the component (B) to generate an active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, the types of ligands of X ²¹ and Y ²¹ are not limited, and hydrogen, halogen groups, hydrocarbon groups having 1 to 20 carbon atoms, and carbons are independent of each other. 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.

Further, Q ²¹ is a bonding group that bridges two conjugated five-membered ring ligands, and is a silylene having a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. It is a gelmilene group having a group or a hydrocarbon group having 1 to 20 carbon atoms, and is preferably a substituted silylene group or a substituted gelmilene 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, diphenylcilylene, methylphenylcilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgelmylene, diethylgermylene, diphenylgermylene and methylphenylgermylene.

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

Non-limiting examples of the metallocene compound represented by the above general formula (4) include the following.
However, only representative example compounds are described, avoiding a large number of complicated examples. Further, although the compound in which the central metal is hafnium is described, it is obvious that a similar zirconium compound can be used, and various ligands, cross-linking groups or co-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-hydroazulenyl}] 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-Hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazulenyl}] 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-hydroazulenyl}] 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-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethyl Silyrenbis {2-methyl-4- (2-chloro-4-biphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (9-phenanthril) -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}] Hafniu M, 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'-dimethylgermilenebis {2-methyl-4- (2-fluoro-4-biphenyl) ) -4-Hydroazurenyl}] hafnium, dichloro [1,1'-dimethylgelmilenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'- (9-Silafluorene-9,9-diyl) Bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Hafnium, dichloro [1,1'-dimethylsilylenebis {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-hydroazurenyl}] hafnium, etc. Can be mentioned.

Of these, preferably dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4 -Hydroazulenyl}] phenylium, dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] phenylium, 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.

Further, 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- Hydroazulenyl}] Hafnium, Dichloro [1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] 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-exchangeable layered silicate.
(I) Types of Ion-Exchangeable Layered Silicates In the present invention, the ion-exchangeable layered silicates (hereinafter, simply abbreviated as silicates) used as raw materials have surfaces formed by ionic bonds and the like, which have a binding force to each other. A silicate compound having a crystal structure stacked in parallel and having exchangeable ions contained in the compound. Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (quartz, cristobalite, etc.) other than ion-exchange layered silicates, but they are included. It may be. Depending on the type, amount, particle size, crystallinity, and dispersed state of these impurities, it may be preferable to pure silicate or higher, and such a complex is also included in the component (B).
The raw material of the present invention refers to a silicate in a stage prior to the chemical treatment of the present invention, which will be described later. Further, the silicate used in the present invention is not limited to a naturally produced one, and may be an artificial synthetic product. They may be included.

Specific examples of silicates include the following layered silicates described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995).
That is, montmorillonite, sauconite, byderite, nontronite, saponite, hectorite, stevensite and other smectites, vermiculite and other vermiculite, mica, illite, sericite, glauconite and other mica, attapargit, sepiolite, parigolskite. , Bentonite, pyrophyllite, talc, chlorite group, etc.

The silicate used as a raw material in the present invention is preferably a silicate having a 2: 1 type structure as a main component silicate, more preferably a smectite group, and particularly preferably montmorillonite. The type of the 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 that it can be obtained relatively easily and inexpensively as an industrial raw material.

(Ii) Chemical Treatment of Ion-Exchangeable Layered Silicate The ion-exchangeable layered silicate of the catalyst component (B) according to the present invention can be used as it is without any special treatment, but it is preferable to carry out chemical treatment. .. Here, as the chemical treatment of the ion-exchangeable layered silicate, either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the structure of clay can be used, and specifically, an acid. Examples include treatment, alkali treatment, salt treatment, and organic substance treatment.

<Acid treatment>:
The acid treatment can remove impurities on the surface and elute some or all of the cations such as Al, Fe, and Mg in the 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.
The number of salts (described in the next section) and acids used in the treatment may be two or more. The treatment conditions with salts and acids are not particularly limited, but 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 under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates is eluted. In addition, salts and acids are generally used in aqueous solutions.
In the present invention, a combination of the following acids and salts may be used as the treatment agent. Further, it may be a combination of these acids and salts.

<Salt treatment>:
In the present invention, 40% or more, preferably 60% or more of the cations of the exchangeable Group 1 metal contained in the ion-exchangeable layered silicate before being treated with salts are dissociated from the salts shown below. It is preferable to exchange ions with cations.
The salts used in the salt treatment for the purpose of such ion exchange are a group consisting of a cation containing at least one atom selected from the group consisting of groups 1 to 14 atoms, a halogen atom, an inorganic acid and an organic acid. A compound consisting of at least one selected anion, and more preferably a cation containing at least one atom selected from the group consisting of groups 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 ), It is a compound consisting of 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 .

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 , sulfonyl ₄ , Mg ( Examples thereof include PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , and MgC ₄ H ₄ O ₄ .
In addition, 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.

In addition, 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 , FeF3 , 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.

<Alkaline treatment>:
In addition to the acid and salt treatments, the following alkali treatments and organic matter treatments may be performed as necessary. Examples of the treatment agent used in the alkaline treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , and Ba (OH) ₂ .

<Organic matter treatment>:
In addition, examples of the organic treatment agent used for the treatment of organic substances include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
In addition to the anions exemplified as the anions constituting the salt treatment agent, examples of the anions constituting the organic matter treatment agent include hexafluoroborate, tetrafluoroborate, and tetraphenylborate. It is not limited to these.

Further, these treatment agents may be used alone or in combination of two or more. 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 in the middle of the treatment. Further, the chemical treatment can be performed a plurality of times using the same or different treatment agents.

These ion-exchangeable layered silicates usually include adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and the interlayer water and use it as the component (B).
The method for heat-treating the adsorbed water and the interlayer water of the ion-exchangeable layered silicate is not particularly limited, but it is necessary to select the conditions so that the interlayer water does not remain and the structure is not destroyed. The heating time is 0.5 hours or more, preferably 1 hour or more. At that time, the water content of the component (B) after removal is preferably 3% by weight or less when the water content when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight. Is preferably 1% by weight or less.

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

The ion-exchangeable layered silicate can be treated with the component (C) described later before forming a catalyst or using it as a catalyst, which is preferable. The amount of the component (C) used with respect to 1 g of the ion-exchangeable layered silicate is not limited, but is usually 20 mmol or less, preferably 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, and the treatment temperature is usually 0 ° C. or higher and 70 ° C. or lower, and the treatment time is 10 minutes or longer and 3 hours or shorter. It is also possible and preferable to wash after the treatment. As the solvent, a hydrocarbon solvent similar to the solvent used in the prepolymerization or slurry polymerization described later is used.

Further, as the component (B), it is preferable to use spherical particles having an average particle size of 5 μm or more. As long as the shape of the particles is spherical, a natural product or a commercially available product may be used as it is, or a particle whose shape and particle size are controlled by granulation, fragmentation, separation or the like may be used.

Examples of the granulation method used here include a stirring granulation method and a spray granulation method, but commercially available products can also be used.
In addition, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used for granulation.
The spherical particles obtained as described above preferably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and formation of fine powder in the polymerization step. 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 suitable.
Needless to say, in the present invention, the compounds represented by this formula can be used alone, in combination of a plurality of 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, alkoxy group, or amino group. q represents an integer of 1 to 3 and p represents an integer of 1 to 2. As R ^15, the alkyl group is preferable, and Z is, it is chlorine in the case of halogen, in the case of the alkoxy group is an alkoxy group having 1 to 8 carbon atoms, 1 to the number of carbon atoms in the case of the amino group An amino group of 8 is preferred.

Specific examples of the organic aluminum 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, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and alkylaluminum hydride with p = 1 and q = 3 are preferred. More ^preferably trialkylaluminum ^{R 15} is 1 to 8 carbon atoms.

(D) Formation / prepolymerization of catalyst The catalyst according to the present invention is formed by contacting each of the above components simultaneously or continuously, at one time or multiple times in a (preliminary) polymerization tank. Can be done.
Contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between −20 ° C. and 150 ° C. As the contact order, any combination for the purpose is possible, and particularly preferable ones are as follows for each component.
When the component (C) is used, before the component (A) and the component (B) are brought into contact with each other, the component (A) or the component (B), or both the component (A) and the component (B) The component (C) is brought into contact with the component (C), or the component (A) and the component (B) are brought into contact with each other at the same time, or the component (C) is brought into contact with the component (C), or the component (A) and the component (B) are brought into contact with each other. Although it is possible to bring the component (C) into contact with the component (C) later, a method of contacting the component (A) with the component (C) before contacting the component (A) with the component (B) is preferable.
Further, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

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

The ratio of the component [A-1] to the component [A-2] used in the present invention is arbitrary as long as it satisfies the characteristics of the propylene polymer, but of each component [A-1] and [A-2]. The molar ratio of the transition metal of [A-1] to the total amount is preferably 0.30 or more and 0.99 or less.
From the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by partially copolymerizing the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, the very high molecular weight component, the branch (amount, length, Distribution) can be controlled, thereby controlling the melt properties such as strain hardening degree, melt tension, and melt ductility.
In addition, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen used.
It is particularly preferably 0.40 or more, and further preferably 0.5 or more, for the production of a propylene-based polymer for applications that require higher melt properties and higher catalytic activity. 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 contacting an olefin with the catalyst and polymerizing in a small amount. By performing the prepolymerization treatment, it is possible to prevent the formation of a gel when the main polymerization is performed. It is considered that the reason is that the long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is carried out, and thereby the melt property can be improved.

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

Further, it is also possible to allow a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania to coexist at the time of or after the contact of each of the above components.

(E) Use of catalyst / Propylene polymerization As the polymerization mode, any mode is adopted as long as the monomer for olefin polymerization containing the above-mentioned component (A), component (B) and component (C) is in efficient contact with each other. obtain.
Specifically, the slurry method using an inert solvent, the so-called bulk method in which propylene is used as a solvent without substantially using an inert solvent, the solution polymerization method, or each monomer is made into a gas state substantially without using a liquid solvent. The vapor phase method for keeping can be adopted. Further, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, multi-stage polymerization of two or more stages is also possible.

In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the 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.
Further, when gas phase polymerization is used, 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, it 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.
Further, when gas phase polymerization is used, it is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. 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 modifier and as an auxiliary for the activity improving effect.
Hydrogen is preferably used in a feed ratio of 0 to 1 mol% with respect to propylene, preferably 0.0001 mol% or more, and more preferably 0.001 mol% or more.
By changing the amount of hydrogen used, in addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, distribution) It is possible to control the melt properties such as the degree of strain hardening, the melt tension, and the melt ductility.

Further, in addition to the propylene monomer, copolymerization may be carried out using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer. 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 types of the above comonomer 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-based polymer (A) according to the present invention in a well-balanced manner in terms of melt properties and catalytic activity, it is preferable to use ethylene in an amount of 5 mol% or less. In order to obtain a polymer having particularly high rigidity, it is preferable to use ethylene so that the 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 macromer is generated by a special chain transfer reaction generally called β-methyl elimination, and in the present invention, the component [A-1] having a specific structure is relatively. In the low temperature range (40 ° C to 80 ° C), the selectivity of the β-methyl elimination reaction during the growth arrest reaction is high, and the ratio of the β-methyl elimination reaction to the polymer growth reaction is the same as that of the complex having the conventional structure. In comparison, it has been found to be large.
In the past, 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 vapor phase polymerization can be used, and practical pressure conditions (1.0 to 3.0 MPa) and temperature conditions (40 ° C.) can be used. It was found that the production was possible under (~ 80 ° C.).

Furthermore, surprisingly, by adding hydrogen, the chain transfer reaction by hydrogen becomes predominant over the β-methyl elimination reaction in the conventional method, whereas the cause is unknown, but it relates to the present invention. It was found that the method for producing the propylene polymer (A) has a feature that the change in the balance between macromer formation and growth reaction is small even when hydrogen is added, and that the selectivity of macromer is almost unchanged even in the presence of hydrogen. .. Moreover, hydrogen has an activity improving effect.
This means that, in contrast to the conventional case where multi-stage polymerization in which macromer copolymerization is performed must be performed after undergoing a macromer formation step under special conditions (low pressure, high temperature, no hydrogen addition), the component [A-2] ], It was found that the macromer formation step and the macromer copolymerization step can be performed under the same conditions, that is, simultaneous polymerization and single-stage polymerization can be performed.

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

However, in the present invention, a component having a specific structure having a macromer-forming ability [A-1] and a component having a specific structure having a high-molecular-weight macromer copolymerization ability [A-2] are combined by a specific method. By using it as a catalyst, it is an industrially effective method such as bulk polymerization and gas phase polymerization, especially for single-stage polymerization under practical pressure and temperature conditions, and by using hydrogen as a molecular weight modifier. It is possible to produce the long-chain branched-containing propylene-based polymer (A) having the above-mentioned physical properties.
Further, conventionally, it has been necessary to increase the branch generation efficiency by lowering the crystallinity by using a component having low stereoregularity, but in the method of the present invention, a component having sufficiently high stereoregularity is sided. It has become possible to introduce it 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 a catalyst for propylene polymerization composed of the organic aluminum component (b) are preferable. Further, it is more preferable that a Ziegler-Natta catalyst formed from a solid catalyst component (a) containing titanium, magnesium, halogen and an electron donor as essential components and an organoaluminum component (b) is used for the above polymerization. ..

Further, it is preferable to use the solid catalyst component (a) obtained by contacting the following (i), (ii), (iii) and (iv).
(I) A solid component containing titanium, magnesium and halogen as essential components (ii) An organic substance containing two or more Si-OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms). Silicon compound (iii) Vinyl silane compound (iv) Organic metal compound of group I-III metal

<Component (i)>
Component (i) is a raw material solid component containing titanium, magnesium and halogen. All of these three elements (three components) of titanium (Ti) -magnesium (Mg) -halogen are contained as essential components. Here, "containing as an essential component" means that in addition to the three components listed, other elements for purpose may be contained, and each of these elements exists as an arbitrary compound for purpose. It indicates that they may exist, and that these elements may exist as bonds to each other. The raw material solid components themselves, including titanium, magnesium and halogen, are known. For example, Japanese Patent Application Laid-Open No. 53-456888
No. 54-3894, No. 54-31092, No. 54-39483, No. 54-94591, No. 54-118484, No. 54-131589, No. 55-75411, No. 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 No. 58-27732, No. 58-32604, No. 58-32605, No. 58-67703, No. 58-117206, No. 58-127708, No. 58-183708, No. 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, Japanese Patent Application Laid-Open No. 1-790203, 1-139601, 1-215806, 7- No. 258328, No. 7-269125, No. 11-21309, and the ones described in each publication are used.

In addition, those obtained by treating these substances with a tungsten or molybten compound can also be mentioned.

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

The titanium compound serving as the titanium source of the component (i) is a general formula Ti (OR ² ) _4-q X _q (where R ² is a hydrocarbon group, preferably having about 1 to 10 carbon atoms). Yes, X represents a 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 (On-C ₄ H ₉ ) Cl ₃ , Ti (On-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 (On-C ₆ H ₁₃ ) ₄ , Ti (On-C ₈ H ₁₇ ) ₄ , Ti ( OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ) _{4 and the} like can be mentioned.

Furthermore, _'(wherein, X _4' is halogen a is.) TiX can also be used a molecular compound obtained by reacting an electron donor which will be described later 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, Examples thereof include TiCl ₄・ C ₆ H ₅ COCl, TiCl ₄・ C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・ Cl COC ₂ H ₅ , TiCl ₄・ C ₄ H ₄ O and the like.

In addition, TiCl ₃ (including those obtained by reducing TiCl ₄ with hydrogen, reduced with aluminum metal, reduced with an organic metal compound, etc.), 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 above-mentioned halogen compounds of magnesium and / or titanium, but other halogen sources such as aluminum halides such as AlCl ₃ and boron such as BCl ₃ are used. Halogenates, silicon halides such as SiCl ₄ , phosphorus halides such as PCl ₃ and PCl ₅ , tungsten halides such as WCl ₆ , and molybdenum halides such as MoCl ₅ are supplied from known halides. You can also do it. 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 electron donors (internal donors) that can be used in the production of the raw material solid component (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, and the like. Examples thereof 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 sulfonic acid esters. it can.

More specifically, (a) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropylbenzyl alcohol, (b). ) Phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methylethylketone, methylisobutylketone, acetophenone, Ketones with 3 to 15 carbon atoms such as benzophenone, (d) aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthoaldehyde

(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 chloracetate, 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 , Methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide and other organic acid monoesters, Alternatively, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylic acid, ethylene carbonate, norbornandienyl-1,2-dimethylcarboxylate, cyclopropane-1 , 2-Dicarboxylic acid-n-hexyl, 1,1-cyclobutanedicarboxylic acid diethyl, and other organic acid polyvalent esters with 2 to 20 carbon atoms,

(F) Inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate, (g) acetyl chloride, benzoyl chloride, toluyl acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl isochloride and other carbon atoms. 2 to 15 acid halides, (ti) 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-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-Dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3- Ethers with 2 to 20 carbon atoms such as diethoxypropane,

(I) Acid amides such as acetate amide, benzoic acid amide, and toluic acid amide, (nu) Methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picolin, tetramethylethylenediamine and other amines. Classes, nitriles such as (le) acetonitrile, benzonitrile, tolnitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy-2-phenylpropi Alkoxy ester compounds such as ethyl oxide, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate,

Ketoester compounds such as (W) 2-benzoylethyl benzoate, 2- (4'-methylbenzoyl) ethyl benzoate, 2-benzoyl-4,5-dimethylethyl benzoate, (f) methyl benzenesulfonate, benzene Examples thereof include sulfonic acid esters such as ethyl sulfonate, ethyl p-toluenesulfonic acid, isopropyl p-toluenesulfonic acid, p-toluenesulfonic acid-n-butyl, and p-toluenesulfonic acid-s-butyl.

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

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

(C) The reaction product obtained by contacting a titanium halogen compound and / or a halogen compound of silicon and an electron donor with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound is inactive. A method of washing with an organic solvent. As the polymer silicon compound used here, the one represented by the 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 indicates a degree of polymerization such that the viscosity of this polymer silicon compound is about 1 to 100 centi-stokes.
Specifically, methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 , 9-Pentamethylcyclopentasiloxane and the like are preferable.

(D) The 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 the solid component precipitated with the halogenating agent or the titanium halogen compound, or separately. How to make contact.
(E) An organic magnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donor is brought into contact with the halogenating agent, a reducing agent, etc. , How to contact each separately.
(F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor, or contacting them separately.

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

<Ingredient (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 a bond residue other than the -OR ¹ group bonded to the silicon atom, a bond residue selected from hydrogen, halogen, a hydrocarbon group (for example, an alkyl group, a cycloalkyl group, an aryl group, etc.), a siloxy group, etc. It is normal to use what you have.

A preferable organic silicon compound has at least one hydrocarbon group, and more preferably, a carbon atom adjacent to the silicon atom, that is, an 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 organic silicon compound of the 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 (CH 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 ) Si (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 (O CH 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 ) (OCH ₃ ) ₂ , (CH ₃ ) ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) _{2 and the} like can be mentioned.

Of these, the preferred ones 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)>
The component (iii) preferably used to form the solid catalyst component (a) is a vinylsilane compound. As a 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) 2 -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- SiC, (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.

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

The remaining valences (if any) of the metal of an organic metal compound in which at least one of the valences is filled with an organic group are hydrogen atom, halogen atom, hydrocarbon group (hydrocarbon group has 1 to 1 carbon atoms). It is filled with about 10 (preferably about 1 to 6), or the metal (specifically, -O-Al (CH ₃ )-) of methylarmoxane via a carbon atom, or the like.

Specific examples of such organic metal compounds include (a) organic lithium compounds such as methyllithium, n-butyllithium, and tertiary butyllithium, and (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, and butylmagnesium. Organic magnesium compounds such as chloride and tertiary butylmagnesium bromide, (c) organic zinc compounds such as diethylzinc and dibutylzinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n -Octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, diisobutylaluminum monochlorodeide, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, methylaluminoxane, etc. Organic aluminum compounds can be mentioned.
Of these, organoaluminum compounds are particularly preferable.

<Manufacturing of solid catalyst component (a)>
The solid catalyst component (a) is such that the components (i) to (iv) constituting the component (a) and any component used as necessary are brought into contact with each other stepwise or temporarily, in between. It can be produced by washing with an organic solvent and / or finally.
Specifically, (a): a method of contacting the component (i) with the component (iii), then contacting the component (ii) and the component (iv), and finally cleaning, (b): the component ( A method of contacting the component (iii) and the component (iv) after contacting the i) with the component (ii) for cleaning, (c): contacting the components (i), (ii), and (iii) at the same time. Later, a method of contacting the component (iv) and cleaning is adopted.

The solvent used for cleaning the organic solvent includes an inert organic solvent such as an aliphatic or aromatic hydrocarbon solvent (for example, hexane, heptane, toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (for example, -n-chloride). Butyl, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.) can be mentioned.

The contact conditions for each component constituting the solid catalyst component (a) need to be carried out in the absence of oxygen, but may be arbitrary as long as the effects of the present invention are recognized, but in general, 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 rotary ball mill, a vibration mill, a jet mill, a medium stirring crusher, and a method of contacting by stirring in the presence of an inert diluent. Examples of the Inactive Diluent used at this time include aliphatic or aromatic hydrocarbons, halo hydrocarbons, and polysiloxane.

The amount ratio of the amount of each component used to constitute the solid catalyst component (a) can be arbitrary as long as the effect of the present invention is recognized, but is generally preferably within the following range.
The amount of the titanium compound used as the component (i) is 0.0001 to 1,000, more preferably 0.01 to 10 in terms of molar ratio (Ti / Mg) with respect to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount used is 0.01 in terms of molar ratio to the amount of magnesium used, regardless of whether the titanium compound and / or magnesium compound contains halogen. It is preferably ~ 1,000, more preferably 0.1 to 100. The amount of the electron donor used is preferably 0.001 to 10 in terms of molar ratio (halogen / Mg) with respect to the amount of the magnesium compound used, and more preferably 0.01 to 5.

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

Further, 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. Alkylaluminum hydride, alkylaluminum alkoxides such as diethylaluminum ethoxide, alumoxane such as methylalmoxane and tetrabutylalmoxane, reactants of trialkylaluminum and dibutyl methylboronate, composite organoaluminum compounds such as lithiumaluminum tetraethyl. Be done. It is also possible to mix and use two or more of these.

The blending amount of the propylene-based 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 preferably 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, the uniform stretchability is inhibited.

The polymerization method of the propylene-based polymer (B) of the present invention includes a slurry method using an inert solvent, a solution method, a vapor phase method using substantially no solvent, or a polymerization monomer in the presence of the catalyst. A bulk polymerization method using the above as a solvent can be mentioned. As a method for obtaining the propylene-based polymer (B) used in the present invention, for example, a desired polymer can be obtained by appropriately controlling the distribution of molecular weight and crystallinity by adjusting the polymerization temperature and the amount of comonomer. ..
Such a propylene-based polymer (B) can also be appropriately selected and used from those commercially available as polypropylene. Examples of commercially available products include "Novatec" manufactured by Japan Polypropylene Corporation.

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 organosilicon containing two or more Si-OR ¹ bonds exemplified in the component (ii). Compounds and the like can be exemplified.
Of these, when tert-butylmethyldimethoxysilane is used as an external donor during production, the isotactic pentad fraction (mmmm fraction) of the propylene-based polymer is further increased, and the rigidity is improved.

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

As the polymerization form, it is preferable to carry out by multi-stage polymerization in which the raw material propylene (and ethylene or the like) is polymerized in a vapor phase state.
Each step of the gas phase polymerization step may be any number of steps.

Examples of the reactor for polymerization include a fluidized bed reactor, a horizontal reactor having a stirring blade, and the like, regardless of the shape and structure.

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, but is additionally and supplied to the second and subsequent polymerization tanks. It doesn't matter if it is done.

In the first polymerization tank, a predetermined amount of propylene is continuously supplied under a constant polymerization pressure and temperature, and the catalyst and hydrogen are controlled so that the ratio of the propylene to hydrogen becomes constant. The produced polymer is sequentially transferred to the next-stage polymerization tank together with the unreacted raw material. The catalyst is not supplied to the second and subsequent polymerization tanks, and the catalyst contained in the polymer transferred from the polymerization tank in the previous stage is used for polymerization. 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 polymerization tank in the previous stage is transferred to the reactor in the next stage and used.

The polymerization pressure is not particularly limited, but is usually 0.2 to 5 MPa, preferably about 0.3 to 2 MPa. The polymerization pressure of 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 of each stage may be the same or different.

The polymerization time is not particularly limited, but it is usually carried out in 10 minutes to 10 hours.
Further, the polymerization time of each of the multiple stages is not particularly limited, but is set to, for example, 30 minutes for the first stage, 30 minutes for the second stage, and 1 hour for the third stage.

The propylene-based polymer (B) has a melting point measured by DSC at 150 to 170 ° C., preferably in the range of 155 to 165 ° C. If the melting point falls below this range, the rigidity of the sheet decreases, and if it exceeds this range, the transparency decreases.
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. The range of 0 to 20% by weight is particularly preferable, and the range of 0 to 10% by weight is most preferable. If the blending amount of (B) exceeds the above, uniform stretchability is inhibited.

In the present invention, the draw 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, and the surface ratio is more preferably 5 to 25 times, and 7 to 20 times. Stretching is more preferred. If the surface magnification exceeds the above, it is necessary to increase the thickness of the raw sheet, and it may be difficult for the existing equipment to support the sheet forming and stretching processes.

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

[However, in the formula (1), n is an integer of 0 to 2, and R1 to R5 are the same or different, and are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms and 2 to 20 carbon atoms, respectively. Is 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. ]

Commercially available nucleating agents can be used. For example, the product name Gelall MD manufactured by New Japan Chemical Co., Ltd., the product name Mirad 3988 and Mirad NX8000J manufactured by Milliken Co., Ltd., and the like, but Mirad NX8000J is the most preferable.
In addition, you may use these nucleating agents in combination of 2 or more types.

In addition, the propylene-based polymer used in the present invention includes antioxidants, neutralizers, nucleating agents, light stabilizers, ultraviolet absorbers, inorganic fillers, blocking inhibitors, lubricants, antistatic agents, and metal inerts. Various additives that can be usually used for polypropylene, such as agents, peroxides, and colorants, can be blended within a range that does not impair the object of the present invention.
Examples of the antioxidant include a phenol-based antioxidant, a phosphite-based antioxidant, and a thio-based antioxidant, and examples of the neutralizing agent include higher fatty acid salts such as calcium stearate, zinc stearate, and aluminum stearate. And hydrotalcites can be exemplified, and examples of the light stabilizer and the ultraviolet absorber include hindered amines, nickel complex compounds, benzotriazoles, benzophenones and the like.
The propylene-based polymer composition can be used alone as it is, or polypropylene, polyethylene, various types different from the propylene-based polymers (A) and (B), as long as the effects of the present invention are not impaired. It can also be used by adding another polymer such as an elastomer or a petroleum resin.

The propylene-based polymer used in the present invention is a polypropylene-based resin composition containing a predetermined amount of each of the above-mentioned nucleating agent, various additives, and another polymer as required, and is used as a sheet of crystalline propylene polymer. It can also be used for production, which is a preferred embodiment of the present invention. In the polypropylene resin composition, these compounding components are mixed or melted in a mixer such as a Henschel mixer (trade name), a super mixer, a V blender, a tumbler mixer, a ribbon blender, a Banbury mixer, a kneader blender, a uniaxial or biaxial extruder, or the like. It can be prepared by mixing or melt-kneading with 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-based 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 an ethylene-vinyl alcohol copolymer (EVOH) or a polyamide resin and an adhesive layer are arranged is provided on at least one surface of the main layer, a high gloss layer or a low gloss layer is further provided on the outermost layer. It is also possible to arrange a layer having a design property such as a glossy layer.
Further, a surface treatment agent such as an antifogging agent, an antistatic agent, and 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-based resin composition to a known extruder, melting the polypropylene-based resin composition, cooling and solidifying the unstretched sheet, and stretching the unstretched sheet in the biaxial direction.
A known method can be used for producing the unstretched sheet. For example, a method of winding a resin melt-extruded from a T die around a cooling roll, or a method of cooling and solidifying a resin melt-extruded from a circular die by air cooling or water cooling. 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 utilizing a speed difference between rolls, and a pantograph type batch stretching method.
The thickness of the raw sheet using the polypropylene-based 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 secure the sheet wall thickness after stretching, and when the thickness is 4 mm or less, the sheet molding becomes easy.

In addition to a single layer, the raw sheet of the propylene-based polymer mixture can be molded into a multi-layer polypropylene-based sheet using a feed block or a multi-manifold using a plurality of extruders usually used for molding polypropylene. it can.
As a specific method for producing a polypropylene-based sheet, a known uniaxial or a polypropylene-based resin composition in which a polypropylene-based resin composition is mixed with other components (nucleating agent, various additives, another polymer) as necessary is used. After passing through a twin-screw screw extruder and extruding into a sheet from a coat hander die, an air knife, an air chamber, a hard rubber roll, and a steel belt are placed on the surface of the metal roll (where cooling water and oil circulate inside). It can be obtained by pressing with a metal flex roll or a metal roll and cooling and solidifying. Further, both sides of the sheet can be sandwiched between steel belts to be cooled and solidified.
Among such sheet cooling methods, the method of using a metal roll and / or a steel belt and a metal flex roll on both sides of the sheet is the most effective because a sheet surface having less surface irregularities, that is, a sheet having excellent transparency can be obtained. This is the preferred method.

[Molded product]
The molded product of the present invention is a molded product thermoformed using the biaxially stretched polypropylene-based sheet of the present invention.
One side surface of the molded product of the present invention is a molded product that has been vacuum-pneumatically molded using the biaxially stretched polypropylene-based sheet of the present invention at a compressed air pressure of 0.2 MPa or more at a melting peak temperature or lower.

Examples of the heating method in such thermoforming include indirect heating, hot plate heating, and thermal roll heating. If molding is performed at a temperature exceeding the melting peak temperature of the sheet, the transparency, gloss, and wall thickness uniformity of the obtained molded product deteriorate, and molding tends to be impossible.

When thermoforming is performed below the melting peak temperature of the crystalline polypropylene polymer, it is preferably softened by heating at a temperature within a melting peak temperature range of 5 to 30 ° C. from the mold cavity side. It can be molded by vacuum suction and applying an air pressure of 0.2 MPa or more from the opposite side to bring the biaxially stretched polypropylene-based sheet into close contact with the surface of the mold cavity.
When the compressed air pressure exceeds 0.2 MPa, it becomes easy to faithfully obtain the shape of the mold. The compressed air pressure is 0.2 MPa or more, preferably 0.3 MPa or more, and more preferably 0.35 MPa or more.
Further, an assist plug can be provided, which is preferable because the thickness uniformity of the molded product is improved.

[Use of molded product]
Since the molded product of the present invention has excellent 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.

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

1. 1. Evaluation method (1) Melt flow rate (MFR) [Unit: g / 10min]
Propylene-based resins are subject to JIS K7210: 1999 "Plastics-Test Methods for Melt Mass Frolate (MFR) and Melt Volume Frolate (MVR) of Thermoplastics", Method A, Condition M (230 ° C, 2.16 kg load) The ethylene / α-olefin copolymer was measured according to JIS K6922-2: 1997 Annex, and measured at 190 ° C. and a load of 2.16 kg.
(2) Melting point (Tm) and crystallization temperature (Tc)
Using DSC6200 manufactured by Seiko Instruments, a sheet-shaped sample piece was packed in a 5 mg aluminum pan, and the temperature was once raised from room temperature to 200 ° C. at a heating rate of 100 ° C./min, held for 5 minutes, and then 10 ° C./min. The crystallization temperature (Tc) was obtained as the maximum crystal peak temperature (° C.) when the temperature was lowered to 20 ° C., and then the maximum melting peak when the temperature was raised 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)
It was measured and calculated by gel permeation chromatography (GPC) by the method described herein.
(4) Temperature elution separation (TREF)
The TREF measurement method is as described above using the following device.
(I) TREF part TREF column: 4.3 mmφ x 150 mm Stainless steel column Column filler: 100 μm Surface-inactivated 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 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 0.1 ml
Injection inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Iii) Detector 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 1.5 mm Window shape 2φ x 4 mm Oval synthetic sapphire window plate Measurement temperature: 140 ° C
(Iv) Pump section Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd. (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 take-up speed Using Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., the resin is extruded into a string shape under the following conditions, and the tension detected by the pulley when it is taken up by a roller is measured. It was measured as melt tension (MT).
Capillary: 2.1 mm in diameter
Cylinder diameter: 9.6 mm
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 object 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., an orifice diameter of 1.0 mm and a length of 8.0 mm were extruded at 190 ° C. with a load applied, and the load was adjusted so that the extrusion speed was 0.1 g / min. At that speed, the polymer extruded from the orifice was quenched in ethanol and calculated as the value of the strand diameter at that time divided by the orifice diameter. This value correlates with Log (MFR), and when this value is large, it indicates that the product appearance when the swell is large and injection molded is improved.
(7) mm fraction Measured by the method described in the above specification using GSX-400 and FT-NMR manufactured by JEOL Ltd. The unit is%.
(8) Measurement of ethylene content
^{13 A} calibration curve was prepared using C-NMR and measured using IR.
(9) Extensional Viscosity The extensional viscosity was 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-rays.

(11) Standard deviation Measurement was performed according to one of the following evaluation methods.
A go board at 10 mm intervals is stamped in a 50 mm square in the center of the surface of the unstretched raw sheet cut into 95 mm square, and biaxially stretched using a biaxial stretching machine (biaxial stretching test device manufactured by Toyo Seiki Seisakusho Co., Ltd.). (Manufacturing-1), the thickness of the intersections of the stretched board (25 points in total) was measured, and the standard deviation value of the thickness was obtained. The stretching ratio was vertical × horizontal = 4 × 4 times (surface magnification = 16 times).
A go board at 10 mm intervals is stamped in a 50 mm square in the center of the surface of the unstretched raw sheet cut into a 95 mm square, and biaxially stretched using a biaxial stretching machine (KAROIV manufactured by Brookner) (Manufacturing-2). The thickness of the intersections of the stretched board (25 points in total) was measured, and the standard deviation value of the thickness was obtained. The stretching ratio was vertical × horizontal = 3 × 3 times (surface magnification = 9 times).

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

Production Example 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)):
Synthesis of (1-a) 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 the mixture was cooled to −70 ° C. A t-butyllithium-pentane solution (260 ml, 0.38 mol, 1.46 mol / L) was added dropwise thereto. After the dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The mixture was cooled to −70 ° C. again, and a dimethoxyethane solution (100 ml) of triisopropylborate (46 ml, 0.20 mol) was added dropwise thereto. After the dropping, the mixture was stirred overnight while gradually returning to room temperature.

Distilled water (100 ml) was added to the reaction solution, and after stirring for 30 minutes, an aqueous solution of sodium carbonate (150 ml), 4-bromoinden (30 g, 0.15 mol), tetrakis (triphenylphosphino) palladium (5 g, 4) .3 mmol) were added in sequence, then the low boiling component was removed and heated at 80 ° C. for 5 hours.
The reaction solution was poured into ice water (1 L), ether extraction was performed three times from the reaction solution, 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 evaporated under reduced pressure, and the residue was purified on a silica gel column to obtain 4- (4-t-butylphenyl) -indene (37 g, 98% yield) 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, N-bromosuccinimide (35 g, 0.20 mol) was gradually added thereto, and the mixture was stirred as it was at room temperature for 1 hour.
The reaction solution was poured into ice water (1 L), and extraction was performed with toluene three times. The toluene layer was washed with saturated brine, p-toluenesulfonic acid (4.3 g, 22 mmol) was added, and the mixture was heated under reflux for 2 hours while removing water.
The reaction solution was transferred to a separating funnel and washed with saline solution until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was evaporated under reduced pressure, and the residue was purified on 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 Methylfuran (13.8 g, 0.17 mol) in a 1000 ml glass reaction vessel. , Dimethoxyethane (400 ml) was added, and the mixture was cooled to −70 ° C. A n-butyllithium-hexane solution (111 ml, 0.17 mol, 1.52 mol / L) was added dropwise thereto. After the dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled to 70 ° C. again, and a dimethoxyethane solution (100 ml) containing triisopropylborate (41 ml, 0.18 mol) was added dropwise thereto. After the dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water (50 ml) was added to the reaction solution, and after stirring for 30 minutes, an aqueous solution of 54 g of sodium carbonate (100 ml), 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 the mixture was heated while removing the low boiling component and heated at 80 ° C. for 3 hours.
The reaction solution was poured into ice water (1 L), ether extraction was performed three times from the reaction solution, 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 is filtered, the solvent is evaporated under reduced pressure, purified on a silica gel column, recrystallized from hexane, and 4- (4-t-butylphenyl) -2- (5-methyl-2-furyl)-. Inden (30.7 g, yield 66%) was obtained as colorless crystals.

(1-d) Synthesis of 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. A n-butyllithium-hexane solution (42 ml, 67 mmol, 1.60 mol / L) was added dropwise thereto. After the dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled to −70 ° C. again, 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 the dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, and the mixture was transferred to a separating funnel and washed with saline solution until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to obtain dimethylbis (2- (5-methyl-2-furyl) -4- (4-t-butylphenyl))-indenyl). A pale yellow solid of silane (22 g, yield 92%) was obtained.

(1-e) rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] Hafnium synthesis 500 ml glass To the reaction vessel, 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. It was cooled to −70 ° C. in a dry ice-methanol bath. 16 ml (26 mmol) of a 1.59 mol / liter n-butyllithium-hexane solution was added dropwise thereto. After the dropping, the temperature was returned to room temperature and the mixture was 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 mixture was cooled to −70 ° C. in a dry ice-methanol bath. To that, 4.2 g (13.0 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was evaporated under reduced pressure, recrystallized from dichloromethane / hexane, and dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl)-. Indenyl}] A racemate of hafnium (purity 99% or more) was obtained as a yellow-orange crystal in an amount of 1.3 g (yield 22%).

The identification values of the obtained racemic mixture by proton nuclear magnetic resonance ( ¹ H-NMR) are described below.
[ ^{1 1} H-NMR (CDCl ₃ ) identification result]:
Racemic: δ0.95 (s, 6H), δ1.18 (s, 18H), δ2.09 (s, 6H), δ5.80 (d, 2H), δ6.37 (d, 2H), δ6. 75 (dd, 2H), δ7.09 (d, 2H), δ7.34 (s, 2H), δ7.33 (d, 2H), δ7.35 (d, 4H), δ7.87 (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 described in Example 1 of JP-A-11-240909. It was carried out in the same manner as.

(2) [Catalyst Synthesis Example 1]
(2-1) Chemical treatment of ion-exchangeable layered silicate In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then montmorillonite (Benclay SL manufactured by Mizusawa Chemical Co., Ltd .: average particle size 19 μm) was added as the layered silicate. ) 600 g was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./min 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 then filtration was performed to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to a separable flask to prepare an aqueous solution of lithium sulfate, and the entire amount of the cake-like solid was put into the flask, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./min and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, 1980 g of distilled water was added, and then the reaction slurry was filtered. Further, the reaction slurry was washed with distilled water to pH 3 and filtered to obtain 1150 g of a cake-like solid.
The obtained solid is pre-dried at 130 ° C. under a nitrogen stream for 2 days, then coarse particles of 53 μm or more are removed, and then rotary kiln-dried at 215 ° C. under a nitrogen stream for a residence time of 10 minutes to chemically treat smectite. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81% by weight, Si: 36.63% by weight, Mg: 1.27% by weight, Fe: 1.82% by weight, Li: 0.20% by weight. 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 placed, and heptane (65 mL) was added to prepare a slurry, to which triisobutylaluminum (25 mmol) was prepared. : A heptane solution having a concentration of 143 mg / mL (34.6 mL) was added, and the mixture was stirred for 1 hour, washed with heptane to 1/1000, and heptane was added so that the total volume became 100 mL.
Further, in another flask (volume 200 mL), the rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl)-) prepared in Synthesis Example 1 of the catalyst component (A). 4- (4-t-Butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (solution 1), and the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (45 μmol) prepared in Example 2 was dissolved in toluene (12 mL) (solution 2). ).

After adding triisobutylaluminum (0.6 mmol: 0.83 mL of heptane solution having a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, the above solution 1 is added, and after another 5 minutes, the above solution 2 is added. In addition, the mixture was stirred at room temperature for 1 hour.
Then, 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. Then, the propylene feed was stopped, the temperature was raised to 50 ° C., and residual polymerization was carried out until the pressure in the autoclave reached 0.05 MPa. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.3 mL of heptane solution having a concentration of 143 mg / mL) was added to the remaining portion, and the mixture was stirred for 5 minutes.
The solid was dried under reduced pressure for 2 hours to obtain 27.5 g of a dry prepolymerization catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.75 (prepolymerized catalyst 1).

(3) Production of Propylene Resin (PP-1) After sufficiently replacing the inside of a stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of fully dehydrated liquefied propylene was introduced. After adding 7.8 NL (0.70 g) of hydrogen and 0.47 L of triisobutylaluminum (0.12 mol: 0.47 L of heptane solution having a concentration of 50 g / L) to this, the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst (by weight excluding the prepolymerized polymer) was press-fitted with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was press-fitted, unreacted propylene was purged, and the inside of the autoclave was replaced with nitrogen to terminate the polymerization. The obtained polymer was dried under a nitrogen stream at 90 ° C. for 1 hour to obtain 18.7 kg of the polymer.
The catalytic activity was 7800 gPP / g catalyst. The MFR was 2.3 g / 10 minutes.

(4) Production of propylene resin (PP-2) The same procedure as the production of propylene resin (PP-1) was carried out except that the hydrogen to be added was 9.9 NL (0.88 g), and the weight was 23.5 kg. Obtained coalescence. The catalytic activity was 9800 gPP / g catalyst. The MFR was 9.0 g / 10 minutes.

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

[Example 1]
(1) 100 parts by mass of propylene resin (PP-1) and 0.05 parts by mass of IRGANOX1010 (trade name, manufactured by Ciba Specialty Chemicals) as a phenolic antioxidant as a phosphorus-based antioxidant. 0.1 part by mass of IRGAFOS168 (trade name, Ciba Specialty Chemicals) and 0.03 part by mass of calcium stearate as a neutralizing agent are mixed, sealed with a super mixer, mixed for 3 minutes, and then extruded. The polypropylene-based resin composition 1 was obtained by melt-kneading and pelletizing with a machine.
Table 1 shows various physical properties measured for the obtained pellets.

(2) Production of polypropylene sheet and biaxially stretched sheet-1
The polypropylene sheet obtained by putting the pellets obtained above into an extruder having a screw diameter of 65 mm, heating, melting and plasticizing at a resin temperature of 230 ° C. and extruding from a T-type die is cooled inside with water at 60 ° C. It is sandwiched between a mirror-finished metal cast roll and a mirror-finished metal cast whose inside is similarly cooled with water at 70 ° C., and is continuously taken up at a speed of 2 m / min while being cooled and solidified. A sheet having a thickness of 2.0 mm was obtained.
Then, using this sheet, after heating at 154 ° C. for 6 minutes with a biaxial stretching test device (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 4 × 4 in the vertical and horizontal directions at the same time at a stretching speed of 1.0 m / min. It was stretched to a double to obtain a biaxially stretched sheet.
The above-mentioned evaluation was performed on this biaxially stretched sheet. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the constitution 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 with 25% by weight of a propylene polymer (B: FL4), the heating temperature of the biaxial stretching apparatus. The temperature was set to 158 ° C. in the same manner as in Example 1 to obtain a biaxially stretched sheet.
The above-mentioned evaluation was performed on this biaxially stretched sheet. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the constitution of the present invention was excellent in uniform stretchability.

[Example 3]
A propylene resin (PP-2) was used instead of the propylene resin (PP-1), and the same procedure as in Example 1 was carried out except that the heating temperature of the biaxial stretching apparatus was set to 156 ° C. Got
The above-mentioned evaluation was performed on this biaxially stretched sheet. The results are shown in Table 1.
The biaxially stretched polypropylene sheet satisfying the constitution 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 formulation shown in Table 1 and the heating temperature of the biaxial stretching apparatus.
The biaxially stretched polypropylene sheet which 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) Manufacture of polypropylene sheet and biaxially stretched sheet-2
The pellet obtained in Example 1 was put into an extruder having a screw diameter of 65 mm, and the polypropylene-based sheet obtained by heating, melting and plasticizing at a resin temperature of 230 ° C. and extruding it from a T-shaped die was cooled inside with water at 80 ° C. It is sandwiched between a cooled mirror-finished metal cast roll and a mirror-finished metal cast whose inside is similarly cooled with water at 90 ° C., and is continuously picked up at a speed of 1.0 m / min while being cooled and solidified. A sheet having a width of 700 mm and a thickness of 3.0 mm was obtained.
Next, using this sheet, after heating at 155 ° C. for 3 minutes with a biaxial stretching test device (KAROIV manufactured by Bruckner), the stretching speed is 1.0 m / min at the same time in the vertical and horizontal directions up to 3 × 3 times. It was stretched to obtain a biaxially stretched sheet.
The above-mentioned evaluation was performed on this biaxially stretched sheet. The results are shown in Table 2.
The biaxially stretched polypropylene sheet satisfying the constitution of the present invention was excellent in uniform stretchability.

[Examples 5 to 11]
A biaxially stretched polypropylene sheet was obtained in the same manner as in Example 4 at the formulation shown in Table 2 and the heating temperature of the biaxial stretching machine. The results are shown in Table 2.
The above-mentioned evaluation was performed on these biaxially stretched sheets. The results are shown in Table 2.
The biaxially stretched polypropylene sheet satisfying the constitution of the present invention was excellent in uniform stretchability.

[Comparative Example 3]
A biaxially stretched polypropylene sheet was obtained in the same manner as in Example 4 at the formulation shown in Table 2 and the heating temperature of the biaxial stretching machine. The results are shown in Table 2.
The biaxially stretched polypropylene sheet which 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)

100 to 5% by weight of the propylene-based polymer (A) characterized by satisfying the requirements specified in the following (i) to (vi), and a propylene-based polymer having a melting point of 150 to 170 ° C. measured by DSC. A biaxially stretched polypropylene sheet obtained by biaxially stretching an extruded sheet made of a polypropylene-based resin composition containing 0 to 95% by weight of B).
(I) The melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.5 g / 10 minutes or more and 20 g / 10 minutes or less.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) to 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 components 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 the temperature elution separation (TREF) by orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or lower is 3.0% by weight or less.
(V) ^{13 The} isotactic triad fraction (mm) measured by C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of extensional viscosity is 6.0 or more. The biaxially stretched polypropylene sheet according to claim 1, wherein the propylene-based polymer (A) further satisfies the following requirements (vii) and (viii).
(Vii) (MT230 ° C) ≧ 5 g
[In the formula, MT230 ° C. uses 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. Represents the melt tension when measured under the condition of ° C. ]
(Viii) (MaxDraw) ≧ 10 m / min [In the formula, 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 stretched polypropylene sheet according to claim 1 or 2, wherein the propylene-based 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 length of 8.00 mm and a diameter of 1.00 mmφ, sets the temperature inside 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 rapidly cooled in ethanol, and the strand diameter of the extruded product at that time is divided by the orifice diameter. ] The biaxially stretched polypropylene sheet according to any one of claims 1 to 3, wherein the propylene-based 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 50% higher than the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp). On the lower molecular weight side, H ₅₀ is on the higher molecular weight side than Tp), and when α and β are defined as α = H ₅₀ -Tp and β = Tp-L ₅₀ , α / β is larger than 0.9 and 2 It is less than 0.0. The biaxially stretched polypropylene sheet according to any one of claims 1 to 4, wherein each of MD and TD is stretched 1.5 times or more, and the surface magnification is 3 to 30 times. Any one of claims 1 to 5, wherein 0.1 to 1 part by mass of a nucleating agent represented by the following general formula (1) is blended with 100 parts by mass of the polypropylene-based resin composition. The biaxially stretched polypropylene sheet according to the above.

[However, in the formula, n is an integer of 0 to 2, and R1 to R5 are the same or different, and are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms and alkoxy groups having 2 to 20 carbon atoms, respectively. , 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 the standard deviation of the sheet thickness after stretching is 50 or less. A molded product obtained by thermoforming the biaxially stretched polypropylene sheet according to any one of claims 1 to 8.

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