JP2009299018A - Sheet for polypropylene-based heat-molded and deep-draw molded product therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet for polypropylene-based heat-molding and a deep-draw molded product therefrom excellent in stiffness, transparency and deep drawing properties with slight thickness deviation. <P>SOLUTION: The sheet for polypropylene-based heat-molding and the deep-draw molded product thereof are obtained by a propylene-based resin composition comprising a polymer mixture of 3-100 wt.% of propylene-based polymer (X) satisfying the requirements defined the following (i)-(vi) and 0-97 wt.% of propylene-based polymer (Y), wherein (i) MFR is 0.2-20 g/10 minutes, (ii) a Q value is 3.5-10.5, (iii) a ratio of a component having molecular weight (M) of ≥2,000,000 is ≥0.4 wt.% to less than 10 wt.%, (iv) a component eluted at ≤40°C by TREF is ≤3.0 wt.%, (v) an isotactic triad fraction (mm) is ≥95%, and (vi) the degree (λmax) of strain hardening as measured by elongational viscosity is ≥6.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polypropylene-based thermoforming sheet and its deep-drawn molded article having excellent rigidity and transparency, less uneven thickness and excellent deep-drawability, and more particularly, heat treatment such as vacuum forming or pressure forming. The present invention relates to a polypropylene thermoforming sheet having excellent rigidity and transparency, less uneven thickness, and excellent deep drawability even when a deep draw product is produced by molding, and the deep draw product.

  The thermoforming sheet can be formed into thermoforming bodies such as various packaging containers and blister packages by thermoforming such as vacuum forming or pressure forming, and is widely used for various applications. Among these, vinyl chloride resin sheets and polystyrene sheets have been widely used for these applications because of their excellent vacuum formability and pressure formability. In recent years, interest in environmental problems has increased, and there has been a strong demand to prevent generation of harmful gases when incinerating waste. For this reason, instead of vinyl chloride resin sheets and polystyrene sheets, olefin resin sheets that generate very little toxic gas during incineration have come to be used favorably for thermoformed bodies such as vacuum formed bodies and compressed air formed bodies. It was.

  Among these, the propylene-based resin sheet has a high melting point and is lightweight, and thus can be applied to various applications. Conventionally, as a propylene-based resin for a sheet used for the production of a molded product by a thermoforming method such as a vacuum forming method or a pressure forming method, a propylene homopolymer or Propylene-α-olefin random copolymers have been used, but due to the low melt tension, drooping during preheating in thermoforming is large. Molding defects such as uneven thickness occurred frequently.

In order to solve such problems, a method of blending an ethylene-based resin with a propylene-based resin (for example, see Patent Documents 1 and 2) has been proposed, but the effect of preventing dripping is not always sufficient, When ethylene resin is blended, there arises a problem that heat resistance and rigidity, which are characteristics of propylene resin, are lowered.
Although there is a method of blending high-density polyethylene having relatively high heat resistance and rigidity, it is not preferable because transparency is impaired.
In addition, in order to increase the melt tension of the propylene resin, a method using a very special propylene resin in which the propylene resin has free end long chain branching by electron beam radiation (for example, Patent Documents 3 and 4). See also). Such a propylene-based resin is said to have a higher melt tension than a general propylene-based resin, and is suitable for preventing dripping during thermoforming.
However, since the propylene-based resin has a high crystallization speed, when trying to obtain a thermoformed article or a deep-drawn molded article, a portion such as a corner becomes thin and it is difficult to obtain a uniform and high-quality molded article. Has the disadvantages. In addition, since the propylene-based resin has undergone a special modification process, it is not economical and has a problem with odor, and the resin itself undergoes a crosslinking reaction. It occurs in large quantities and has the disadvantage of being difficult to recycle.

JP 52-136247 A Japanese Patent Laid-Open No. 11-240986 Japanese Patent Laid-Open No. 62-121704 JP-A-2-69533

  The object of the present invention is to provide a polypropylene-based heat which is excellent in rigidity and transparency, with little uneven thickness and excellent deep drawability, even when a deep-drawn molded body is produced by thermoforming such as vacuum forming method or pressure forming method. An object of the present invention is to provide a molding sheet and a deep-drawn molded body thereof.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polypropylene-based thermoforming sheet obtained from a propylene-based resin composition containing a specific propylene-based polymer has very high thermoformability. It has been found that the deep-drawn molded body obtained from the thermoforming sheet has little unevenness and is excellent in rigidity and transparency, and has completed the present invention.

That is, according to the first invention of the present invention, the propylene polymer (X) 3 to 100% by weight satisfying the requirements specified in the following (i) to (vi), and the propylene polymer (Y) 0 to A polypropylene thermoforming sheet characterized in that it is obtained from a propylene resin composition containing 97% by weight of a polymer mixture is provided.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(Iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.

According to a second invention of the present invention, in the first invention, the propylene-based resin composition contains 0.01 to 1 part by weight of a crystal nucleating agent with respect to 100 parts by weight of the polymer mixture. A polypropylene-based thermoforming sheet is provided.
According to the third invention of the present invention, in the first or second invention, the propylene polymer (X) further satisfies the following requirement (vii), and the polypropylene thermoforming sheet is characterized in that: Is provided.
(Vii) (ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

According to a fourth invention of the present invention, in any one of the first to third inventions, the propylene polymer (X) further satisfies the following requirement (viii): A forming sheet is provided.
(Viii) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the propylene-based polymer (Y) is polymerized using a metallocene catalyst and has the following characteristics (i): A polypropylene-based thermoforming sheet characterized by satisfying (iv) is provided.
(I) MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g / 10 min.
(Ii) The melting peak temperature (Tm) measured by the DSC method is 120 to 165 ° C.
(Iii) The molecular weight distribution (Q value: Mw / Mn) measured by the GPC method is 1.5 to 4.5.
(Iv) In the elution curve obtained by temperature rising elution fractionation (TREF), the difference (T ₈₀ -T ₂₀ ) between the temperature (T ₂₀ ) extracted at 20 wt% and the temperature (T ₈₀ ) extracted at 80 wt% It is 10 degrees C or less.
Furthermore, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the polymer mixture comprises 5 to 90% by weight of a propylene polymer (X) and a propylene polymer (Y And 10) to 95% by weight of a polypropylene thermoforming sheet.

According to a seventh invention of the present invention, in any one of the first to sixth inventions, the tensile elastic modulus is 1000 Mpa or more, the HAZE is 15% or less, and the draw-down holding time is 10 seconds or more. There is provided a polypropylene-based thermoforming sheet.
According to the eighth invention of the present invention, in the second invention, the crystal nucleating agent is an aromatic carboxylic acid metal salt, an aromatic phosphate metal salt, a sorbitol derivative, an amide nucleating agent, or a rosin. A polypropylene thermoforming sheet is provided that is at least one selected from the group consisting of metal salts.
Furthermore, according to the ninth invention of the present invention, it is obtained by thermoforming the polypropylene thermoforming sheet according to any one of the first to eighth inventions, and has a drawing ratio of 0.5 or more and a minimum thickness. A deep-drawn molded article having a rate of 40% or more is provided.

The present invention relates to a polypropylene-based thermoforming sheet comprising a propylene-based resin composition containing a specific propylene-based polymer (X) as described above, and preferred embodiments include the following. Is done.
(1) The polypropylene thermoforming sheet according to any one of the first to eighth aspects, wherein the propylene polymer (X) further satisfies the following requirements (ix) and / or (x).
(Ix) (MT230 ° C.) ≧ 5 g
[In the formula, MT230 ° C. is measured using a melt tension tester, capillary: diameter 2.1 mm, cylinder diameter: 9.6 mm, cylinder extrusion speed: 10 mm / min, winding speed: 4.0 m / min, temperature: 230 It represents the melt tension when measured under the condition of ° C. ]
(X) (MaxDraw) ≧ 10 m / min [where MaxDraw (maximum winding speed) is the winding speed immediately before the resin breaks when the winding speed is increased in the measurement of the melt tension. To express. ]
(2) The polypropylene thermoforming sheet according to any one of the first to eighth aspects, wherein the sheet thickness is 0.15 to 3 mm.
(3) In any one of the first to eighth inventions, the sheet has at least one resin layer selected from a gas barrier resin layer, an adhesive resin layer, a recycled resin layer, or a candle resin layer on at least one surface of the sheet. Polypropylene thermoforming sheet.

  Since the polypropylene-based thermoforming sheet of the present invention is excellent in thermoformability, particularly deep drawability, the deep-drawn product obtained from the thermoforming sheet is excellent in rigidity and transparency, and has uneven thickness. There are few, and it can utilize suitably for packaging containers etc., such as industrial products, food supplies, and daily necessities.

It is a figure which shows an example of the molecular weight distribution curve in GPC of the propylene-type polymer (X) based on this invention. It is a figure of the description of the base line of a chromatogram in GPC, and an area. It is a figure which shows an example of the molecular weight distribution derived from [A-1] in GPC of the propylene-type polymer (X) which concerns on this invention, and [A-2]. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer. It is a figure explaining the correlation of ME (memory effect) and MFR of propylene polymer (X) concerning the present invention. It is a general view showing the relationship between the amount of sag of the polypropylene thermoforming sheet and the heating time in the evaluation of resistance to drawdown.

The polypropylene-based thermoforming sheet of the present invention includes the following (i) to (vi), or in addition to them, (vii) and / or (viii), or in addition to them, (ix) and / or A propylene resin composition comprising a polymer mixture obtained by mixing 3 to 100% by weight of propylene polymer (X) having the characteristics and properties of (x) and 0 to 97% by weight of propylene polymer (Y) This is a polypropylene thermoforming sheet obtained from the product.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(Iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.

(Vii) (ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]
(Viii) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0.

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

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

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

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

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

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

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

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

The propylene polymer (X) showing the improved melt properties of the present invention has a trace amount of branched components as a result of ¹³ C-NMR measurement, and the amount thereof is about 0.1.
On the other hand, if the amount of branching is too large, there is a concern that gel is generated and the appearance of the molded product is impaired. Furthermore, there is a problem that when the film is stretched at a high speed at the time of molding, so-called melt ductility is deteriorated, that is, the melt breaks. Therefore, the upper limit of the number of branches is 0.4 or less, preferably 0.2 or less. The lower limit is 0.01 or more.
Even in the case of using the current ¹³ C-NMR of high magnetic field NMR, it is difficult to determine with a small amount of about 0.1 unless measurement is performed for a very long time. When the amount of branching was small, instead of this, branching was evaluated by a more sensitive rheological method. As a result, the obtained strain hardening degree (λmax) is defined to be 6.0 or more.

In addition, the propylene polymer (X) according to the present invention is required to have a branching length of 7000 or more, which is an entangled molecular weight of polypropylene. When converted into skeleton carbon number, it corresponds to about 400 or more. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. As the branch length becomes longer, the melt physical properties are considered to be further improved.
Therefore, the branched chain length of the propylene-based polymer (X) according to the present invention is 500 or more skeleton carbon atoms (polypropylene molecular weight conversion: 11,000), preferably 1000 skeleton carbon atoms (polypropylene molecular weight conversion: 2. 10,000) or more, and more preferably 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).
The polypropylene molecular weight converted value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Therefore, the branch length of the propylene-based polymer (X) according to the present invention is 11,000 or more, preferably 21,000 or more, more preferably 4.2 in terms of number average molecular weight (Mn) measured by GPC. Replaced with more than 10,000.

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

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

Describing the relationship between the number of branches and the branch distribution, it is generally considered that a large number of branches is necessary in order to improve the melt properties. Japanese Patent Application Laid-Open No. 2007-154121 discloses that the number of branches is 0.1 / A propylene homopolymer having 1000 skeleton carbons or more is disclosed.
However, the strain hardening degree in the measurement of the extensional viscosity of the disclosed propylene homopolymer is less than 6.0, and the strain hardening degree (λmax in the measurement of the extensional viscosity of the propylene-based polymer (X) according to the present invention). ) Is 6.0 or more, the improvement effect is not sufficient. This is because the desired branching component is not sufficiently introduced because it is produced from a single complex, meaning that the effect of improving the melt properties is small even if the number of branches is simply large on average.
The propylene-based polymer (X) according to the present invention does not necessarily have a larger number of branches (average value) than a conventional branched polymer, but by combining a plurality of complexes, the branching is also performed on the high molecular weight side. By introducing it, the melt properties are remarkably improved.

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

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

(2-1) Melt flow rate (MFR):
The propylene-based polymer (X) according to the present invention needs to have a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 Kg of 0.2 to 20 g / 10 minutes.
The melt flow rate (MFR) of the propylene polymer (X) is 0.2 to 20 g / 10 minutes, and if the MFR is less than 0.2 g / 10 minutes, the fluidity is lowered and the rigidity is also lowered. . On the other hand, when the MFR exceeds 20 g / 10 minutes, the melt processability decreases. Moreover, within this range, it is preferably 0.5 to 15 g / 10 minutes, more preferably 0.7 to 10 g / 10 minutes, and particularly preferably 1 to 5 g / 10 minutes.
The melt flow rate (MFR) is a test condition in accordance with JIS K6921-2 “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties”. : A value measured at 230 ° C. and a load of 2.16 kgf.
The melt flow rate (MFR) of the propylene polymer (X) adjusts the temperature and pressure, which are the polymerization conditions of the propylene polymer (X), and the amount of chain transfer agent such as hydrogen added during the polymerization. By controlling, adjustment can be easily performed.

(2-2) Average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC:
The propylene-based polymer (X) according to the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) as measured by gel permeation chromatography (GPC), and Mw / Mn (Q value) is 3. It must be in the range of 5 to 10.5.
The Q value is an index representing the spread of the molecular weight distribution, and the larger the value, the wider the molecular weight distribution. If the Q value is too small, the distribution is narrow, and the balance between melt fluidity and workability becomes poor. Accordingly, the Q value needs to be 3.5 or more, preferably 4.0 or more. More preferably, it is 4.5 or more. On the other hand, if the Q value is too large, the amount of unnecessary (low) molecular weight components increases, and satisfactory physical properties cannot be obtained. Therefore, the Q value needs to be 10.5 or less, preferably less than 8.0, and more preferably less than 7.5.
The average molecular weight and molecular weight distribution (Mw, Mn, Q value) measured by GPC of the propylene polymer (X) can be changed by changing the temperature and pressure conditions of propylene polymerization, or the most common technique is hydrogen, etc. The chain transfer agent can be easily adjusted by adding the chain transfer agent during propylene polymerization. Furthermore, when using 2 or more types of the metallocene complex to be used and a complex, it can control by changing the quantity ratio.

(2-3) Bias of molecular weight distribution obtained from GPC molecular weight distribution curve toward high molecular weight side:
In the molecular weight distribution curve obtained by GPC, the propylene-based polymer (X) according to the present invention has a common logarithm of the molecular weight corresponding to the peak position as Tp and a common logarithm of the molecular weight at a position where the peak height is 50%. L ₅₀ and H ₅₀ (L ₅₀ is lower molecular weight side than Tp, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively. / Β is desirably greater than 0.9 and less than 2.0. Here, α / β is an index representing the deviation of the molecular weight distribution toward the high molecular weight side.
The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created in which the common logarithm of molecular weight (MW) is plotted on the horizontal axis and the relative differential mass of the molecule corresponding to the MW is plotted on the vertical axis.
The molecular weight (MW) referred to here is the molecular weight of individual molecules constituting the propylene homopolymer, and is different from the weight average molecular weight (Mw) of the propylene homopolymer. FIG. 1 is a diagram showing an example of a molecular weight distribution curve. Α and β are obtained from the created graph. In the present invention, as described above, it is desirable that α / β is greater than 0.9 and less than 2.0.

Usually, when uniform polymerization is carried out with a catalyst having a single active site, the molecular weight distribution has the most probable distribution shape. The most probable distribution α / β is calculated as 0.9.
Therefore, the molecular weight distribution of the propylene homopolymer, which is the propylene-based polymer (X) according to the present invention, further spreads to the higher molecular weight side than the molecular weight distribution of the polymer that is uniformly polymerized at a single active site. It means that
If α / β is 0.9 or less, the amount of the high molecular weight component is relatively insufficient, so that the melt tension and swell ratio become small, and the moldability deteriorates. For example, when extrusion foam molding is performed, in the stage where initial bubbles are formed, the lower the viscosity, the more the cores of the bubbles. On the other hand, in the state where the bubble cell is formed and thinned, if the portion is not strong, the bubble is broken, and thus a component having a high molecular weight is required. In order to satisfy such circumstances, it is important that the molecular weight is further spread on the high molecular weight side than on the low molecular weight side.
Accordingly, it is desirable that the propylene-based polymer (X) according to the present invention has α / β larger than 0.9, preferably 1.0 or more, and more preferably 1.1 or more.

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

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

As described above, when the amount of the high molecular weight component is insufficient, the melt tension and the swell ratio are decreased, and the thermoformability is deteriorated. For example, when vacuum forming is performed, the drawdown becomes large, the metal mold is brought into contact with the mold and is bent, and a so-called bridge phenomenon occurs, so that a satisfactory molded product cannot be obtained. Therefore, a component having a high molecular weight is necessary, and the moldability is efficiently improved by containing a small amount of a component having a very high molecular weight. This very high molecular weight component is considered to contain a branched component as described above.
Therefore, the propylene polymer (X) according to the present invention desirably has W (2 million or more) of 0.4% by weight or more, preferably 1.0% by weight or more, and more preferably Is 2.0% by weight or more.
However, when the ratio of this component is too high, the extrusion sheet formability is deteriorated. In addition, since it is a component having a very high molecular weight, a gel is generated, resulting in a problem that the appearance of the molded product is impaired. On the other hand, when the ratio of this component is too high, when the deep drawing is performed at the time of thermoforming, the melt causes breakage, that is, the so-called melt ductility is deteriorated.
Therefore, the propylene polymer (X) according to the present invention desirably has W (2 million or more) less than 10% by weight, preferably less than 6.0% by weight, more preferably 5.0%. Less than% by weight.

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

The weight average molecular weight (Mw), Q value, α / β, and W (over 2 million) values defined above are all obtained by gel permeation chromatography (GPC). Details of the measuring method and measuring equipment are as follows.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

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

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

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

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

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

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

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

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

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

  Moreover, the propylene polymer (X) according to the present invention may have the following partial structure containing an ethylene unit.

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

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

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

The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm) and carbon F (38 in the position irregular substructure [structure (5-a)]). It can be evaluated from ¼ of the sum of the peak areas of resonance around 0.7 ppm.
The peak areas based on carbon A ′ are carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J of the position irregular substructure [structure (5-b) and structure (5-c)] It can be evaluated by 2/5 of the sum of peak areas (resonance around 34.1 ppm) and the sum of peak areas of carbon K (resonance around 33.7 ppm).
The peak area based on the carbon A ″ can be evaluated by the sum of the peak areas of the carbon L (resonance in the vicinity of 27.7 ppm) of the position irregular partial structure [structure (5-d)].
The peak area based on carbon B can be evaluated by carbon J. The peak area based on carbon B ′ can be evaluated by carbon K.
Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
As described above, since the peak areas of mm, mr, and rr can be evaluated, the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center can be obtained according to the above formula (I).

(2-7) Strain hardening degree (λmax) in measurement of elongational viscosity:
The propylene polymer (X) according to the present invention is required to have a strain hardening degree (λmax) of 6.0 or more in the measurement of elongational viscosity.
The strain hardening degree (λmax) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. As a result, when thermoforming is performed, the draw-down resistance is excellent, and uneven thickness at the time of deep drawing is suppressed small.
Therefore, the strain hardening degree is required to be 6.0 or more, preferably 10.0 or more, more preferably 15.0 or more.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
Furthermore, strain hardening is currently considered the most sensitive method for evaluating branching, and it is difficult to evaluate the branched structure directly by ¹³ C-NMR. The degree of strain hardening was used as an index of branching.

In general, in order to show a high degree of strain hardening, a branching length of 7,000 or more, which is an entanglement molecular weight of polypropylene, is required. When converted into skeleton carbon number, it corresponds to about 400 or more. As used herein, skeletal carbon means all carbon atoms other than methyl carbon. As the branch length becomes longer, the melt physical properties are considered to be further improved. In particular, when a longer branched chain is introduced, strain hardening is considered to be detected even in a slower strain rate region in the measurement of elongational viscosity.
Therefore, the branched chain length of the propylene-based polymer (X) according to the present invention is, as described above, a skeleton carbon number of 500 (polypropylene molecular weight conversion: 11,000) or more, preferably a skeleton carbon number of 1000 (polypropylene molecular weight). Conversion: 21,000) or more, and more preferably 2000 or more skeleton carbon atoms (polypropylene molecular weight conversion: 42,000).
As described above, the polypropylene molecular weight conversion value here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC. Therefore, the branch length of the propylene-based polymer (X) according to the present invention is 11,000 or more, preferably 21,000 or more, more preferably 4.2 in terms of number average molecular weight (Mn) measured by GPC. It can be replaced with over 10,000.
The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene polymer (X) can be determined by controlling the selection of two types of metallocene complexes constituting the catalyst used for propylene polymerization, the ratio of the amounts thereof, and the prepolymerization conditions. , 6.0 or more. That is, one of the two types of metallocene complexes is selected so as to easily generate a macromer, and the other is selected so that the macromer can be easily incorporated into the polymer and can generate a high molecular weight polymer. Furthermore, by performing prepolymerization, long chain branches are uniformly distributed among the polymer particles.

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

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

Measurement method 2:
Apparatus: Toyo Seiki Co., Ltd., Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: An extruded strand is prepared at a speed of 10 to 50 mm / min using an orifice having an inner diameter of 3 mm at 180 ° C. using a capillograph manufactured by Toyo Seiki Co., Ltd.

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

(2-8) Memory effect (ME):
In the propylene polymer (X) according to the present invention, the memory effect (ME) preferably satisfies the following formula (I-1).
(ME) ≧ −0.26 × log (MFR) +1.9 (I-1)
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ]

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

The propylene-based polymer (X) according to the present invention has a large ME in MFR match as compared with a conventionally known polymer, as shown in FIG. 5, due to the presence of a branched component in the polymer chain. It is a feature. When the amount of the long-term relaxation component is large, drawdown during thermoforming is prevented, and the propylene polymer (X) according to the present invention is excellent in thermoforming characteristics. More preferably, the following formula (I-2) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.20 (I-2)
More preferably, the following formula (I-3) is satisfied.
(ME) ≧ −0.26 × log (MFR) +2.40 (I-3)

  The memory effect (ME) of the propylene-based polymer (X) controls the selection and combination of the metallocene complexes (to be described later) used in the polymerization of the propylene-based polymer (X), the amount ratio, and the prepolymerization conditions. By doing so, adjustment can be performed.

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

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

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

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

In addition, as described above, when the high molecular weight component is increased or the number of branches is increased, the MT value can be increased, but conversely, the polymer has too many high molecular weight components or the branches are unevenly distributed. Then, the viscosity becomes too high during winding, causing breakage of the string-like material, and MaxDraw does not increase. That is, the melt ductility is deteriorated.
The propylene polymer (X) according to the present invention can have a large MaxDraw while maintaining a high MT by controlling the branched component, and the balance between melt tension and melt spreadability is improved.
Therefore, the propylene polymer (X) according to the present invention has a MaxDraw of 10 m / min or more, preferably 20 m / min or more, and more preferably 30 m / min or more.
It is important for the maximum winding speed (MaxDraw) of the propylene-based polymer (X) to reduce non-homogeneous components such as a gel. In order to obtain a homogeneous propylene-based polymer (X), diene or the like In the macromer polymerization method using no catalyst, adjustment can be performed by controlling the prepolymerization conditions of the catalyst used and the polymerization conditions such as the hydrogen concentration and temperature.

As described above, the propylene-based polymer (X) according to the present invention is a long-chain branched type in which melt spreadability and melt tension are controlled and excellent in balance between physical properties and workability. In contrast to conventional propylene-based polymers, for example, Japanese Patent Application Laid-Open No. 2007-154121 discloses propylene homopolymers having a branch number of 0.1 / 1000 skeleton carbon or more, but distortion in measurement of elongational viscosity. The degree of cure (λmax) is less than 6.0, and even when the degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene-based polymer (X) according to the present invention is 6.0 or more, the improvement in melt properties can be achieved. The effect is not enough. In addition, the commercial product of polypropylene that is crosslinked by electron beam irradiation and has a high degree of long-chain branching (high melt tension polypropylene manufactured by Basel, “PF814”) does not detect the branched carbon of the structural formula (2) described above. The isotactic triad fraction (mm) by ¹³ C-NMR is low (92.5%), and it is considered that molecular cutting and isomerization occur simultaneously with crosslinking upon irradiation with an electron beam. Solvent-soluble components also occur and low molecular weight components are increasing. In addition, as another general method for controlling the molding processing characteristics, control is performed by expanding the molecular weight distribution. However, when the molecular weight distribution is expanded, the low molecular weight component is increased as a result. Demerits such as deterioration of the surface characteristics of the body, deterioration of mechanical properties and heat sealability occur.
However, the propylene-based polymer (X) according to the present invention is controlled by expanding the molecular weight distribution by broadening the molecular weight distribution and introducing a branch, but the low molecular weight component does not increase and the high molecular weight is increased. Since the components increase, the above disadvantages do not occur.
As described above, since the propylene polymer (X) according to the present invention is a long-chain branched type, the physical properties and processability are controlled by controlling the melt ductility and the melt tension not found in the conventional propylene polymer. It has become an excellent balance.

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

That is, a method for producing the long-chain branched propylene-based polymer, wherein the following catalyst components (A), (B), and (C) are used as propylene polymerization catalysts: The manufacturing method of a polymer is mentioned.
(A): at least one from component [A-1] which is a compound represented by the following general formula (a1) and at least one from component [A-2] which is a compound represented by general formula (a2) Type, selected two or more Group 4 transition metal compounds Component [A-1]: Compound represented by general formula (a1) Component [A-2]: Represented by general formula (a2) Compound (B): Ion exchange layered silicate (C): Organoaluminum compound

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

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

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

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

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

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

Among the compounds represented by the general formula (a1), specific examples of preferable compounds are given below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-i [Denyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl) -2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1 '-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1, '-Dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2 -Naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1 -Naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] haf , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4 -(1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilane Rylenebis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) { 2- (5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2 -Thienyl) -4-phenyl-indenyl}] hafnium, and the like.

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

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

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

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

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ²³ and R ²⁴ each independently contain a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5 -Dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like.

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

Q ²¹ is a bonding group that bridges two conjugated five-membered ring ligands, and a silylene having a C 1-20 divalent hydrocarbon group and a C 1-20 hydrocarbon group. Or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.

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

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

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

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

(B) Catalyst component (B)
Next, the catalyst component (B) used for the polymerization of the propylene-based polymer (X) according to the present invention is an ion-exchange layered silicate.
(I) Types of ion-exchangeable layered silicate In the present invention, the ion-exchangeable layered silicate used as a raw material (hereinafter simply abbreviated as “silicate”) means that the surfaces formed by ionic bonds or the like have a binding force to each other. The silicate compound has a crystal structure stacked in parallel with each other, and the contained ions are exchangeable. Most silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. But you can. Depending on the type, amount, particle diameter, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in component (B).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product. You may include them.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(C) Catalyst component (C)
The catalyst component (C) used for the polymerization of the propylene polymer (X) according to the present invention is an organoaluminum compound. As the organoaluminum compound used as the component (C), a compound represented by the general formula: (AlR ¹¹ _q Z _3-q ) _p is appropriate.
In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more, or in combination. In this formula, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively. R ¹¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, and a C 1 atom when it is an amino group. Eight amino groups are preferred.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, R ¹¹ is a trialkylaluminum having 1 to 8 carbon atoms.

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

The amount of the catalyst components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of component (A) used relative to component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (B). The amount of component (C) used relative to component (B) is preferably such that the amount of Al is 0.01 to 1000 mmol, particularly preferably 0.05 to 500 mmol, relative to 1 g of component (B). Therefore, the amount of the component (C) to the component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ in terms of the molar ratio of the transition metal. .

Although the ratio of component [A-1] and component [A-2] used by this invention is arbitrary in the range with which the characteristic of propylene polymer (X) is satisfy | filled, component [A-1] and component [A] -2] is preferably a molar ratio of the transition metal of component [A-1] to the total amount of 0.30 or more and 0.99 or less.
By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt properties such as strain hardening degree, melt tension, and melt spreadability can be controlled. Transition of component [A-1] with respect to the total amount of component [A-1] and component [A-2] in order to produce a propylene polymer having a higher degree of strain hardening efficiently with higher catalytic activity The molar ratio of the metal needs to be 0.30 or more, preferably 0.40 or more, and more preferably 0.50 or more. Further, the upper limit is 0.99 or less, and in order to efficiently obtain the propylene-based polymer (X) according to the present invention with high catalytic activity, it is preferably 0.95 or less, more preferably 0. .90 or less.
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the hydrogen amount.

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

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

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

(E) Use of Catalyst / Propylene Polymerization Any polymerization method may be adopted as long as the olefin polymerization catalyst containing the component (A), component (B) and component (C) is in efficient contact with the monomer. sell.
Specifically, a slurry method using an inert solvent, a so-called bulk method, a solution polymerization method, or a substantially liquid solvent without using an inert solvent as a solvent. A gas phase method can be used. Further, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

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

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.

Furthermore, as a molecular weight regulator and for activity improvement effect, hydrogen is supplementarily used in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene. Can do.
Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.
Therefore, hydrogen should be used in a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. As for the upper limit may be used in an 1.0 × ^{10 -2} or less, preferably 0.9 × ^{10 -2} or less, still more preferably 0.8 × ^{10 -2} or less.

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

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

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

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

However, in the present invention, the component [A-1] having a specific structure having macromer generation ability and the component [A-2] having a specific structure having high molecular weight and macromer copolymerization ability are combined in a specific method. By using it as a catalyst, it is an industrially effective method such as bulk polymerization or gas phase polymerization, particularly in single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It is possible to produce a long-chain branched propylene polymer (X) having the following physical properties:
Conventionally, the branching efficiency was increased only under conditions for producing a polymer with low stereoregularity, but in the method of the present invention, a sufficiently high stereoregularity component can be added to the side chain by a simple method. It became possible to introduce.

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

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

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

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

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

Characteristic (i) MFR:
The melt flow rate (MFR) of the propylene polymer (Y) used in the present invention is 0.5 to 20 g / 10 min, preferably 0.7 to 10 g / 10 min, more preferably 1 to 5 g / 10 min. It is. When the MFR is less than 0.5 g / 10 min, the viscosity of the molten resin is high and the sheet formability is inferior. On the other hand, when the MFR exceeds 20 g / 10 min, the viscosity of the molten resin is low and the drawdown is large during thermoforming. Therefore, it is not preferable.
Here, MFR is a value measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N (2.16 kg).
The melt flow rate (MFR) of the propylene polymer (Y) is the amount of hydrogen added to adjust the temperature and pressure, which are the polymerization conditions of the propylene polymer (Y), or to add a chain transfer agent such as hydrogen during the polymerization. Adjustment can be easily performed by controlling the above.

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

Characteristic (iii) Molecular weight distribution (Mw / Mn):
The molecular weight distribution (Q value: Mw / Mn) measured by the gel permeation (GPC) method of the propylene-based polymer (Y) used in the present invention is preferably 1.5-4. More preferably, it is less than 8-3. Those having Mw / Mn of less than 1.5 are difficult to obtain with the current polymerization technology, whereas if the Q value exceeds 4, the viscosity in the polymer becomes non-uniform and it is difficult to make the foam cell diameter uniform. This is not preferable.
The molecular weight distribution of the propylene polymer (Y) can be adjusted by selecting a catalyst to be used and a polymerization method. For example, when a metallocene catalyst is used, polymerization is performed using a catalyst system in which two or more metallocene catalyst components are used in combination or a catalyst system in which two or more metallocene complexes are used in combination, or two or more stages of multistage polymerization are performed during polymerization. It can be controlled by doing. On the other hand, in order to adjust the molecular weight distribution narrowly, in addition to a method using one type of metallocene catalyst, it is possible to adjust by polymerizing a propylene-based polymer and then melt kneading using an organic peroxide. it can.
Here, molecular weight distribution is calculated | required by the ratio (Q value: Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn), and a gel permeation chromatography similarly to the propylene polymer (X) mentioned above. Obtained by measurement by a graphic (GPC) method.

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

(2) Polymerization method of propylene polymer (Y) The propylene polymer (Y) used in the present invention is preferably polymerized using a metallocene catalyst. Use of polypropylene polymerized with a catalyst other than a metallocene catalyst is not preferable because the molecular weight distribution is wide, the composition distribution is non-uniform, and it is difficult to make the foam cell diameter uniform and fine.

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

  Examples of (i) metallocene compounds include JP-A-60-35007, JP-A-63-130314, JP-A-63-295607, JP-A-1-275609, JP-A-2-41303, and JP-A-2-41303. JP-A-2-131488, JP-A-2-76887, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, and JP-A-8-85708.

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

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

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

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

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

(3) Blending ratio of propylene polymer (X) and propylene polymer (Y) In the polymer mixture constituting the propylene resin composition used for the polypropylene thermoforming sheet of the present invention, the propylene polymer The blending ratio of the polymer (X) and the propylene polymer (Y) is preferably 3 to 100% by weight for the propylene polymer (X) and 0 to 97% by weight for the propylene polymer (Y). Is 5 to 90% by weight of the propylene polymer (X) and 10 to 95% by weight of the propylene polymer (Y). When the blending amount of the propylene-based polymer (X) is less than 3% by weight, the draw-down resistance of the resulting propylene-based thermoforming sheet is lowered.

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

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

4). Other compounding agents In addition to the propylene polymer (X), the propylene polymer (Y), and the crystal nucleating agent, the propylene resin composition used in the polypropylene-based thermoformed sheet molded body of the present invention includes: Other known polymers usually used for polyolefins, antioxidants, neutralizers, light stabilizers, UV absorbers, inorganic fillers, antiblocking agents, lubricants, antistatic agents, metal deactivators, and other polypropylene Various additives such as polymers that can be used in the present invention can be blended within a range that does not impair the object of the present invention.

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

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

III. Polypropylene Thermoforming Sheet The polypropylene thermoforming sheet of the present invention is obtained by extruding a propylene resin composition through a known uniaxial or biaxial screw extruder into a sheet form from a coat solder die. It can be obtained by cooling and solidifying by pressing an air knife, an air chamber, a hard rubber roll, a steel belt, or a metal roll on the surface of the metal roll (in which cooling water or oil circulates inside). It is also possible to cool and solidify both sides of the sheet with a steel belt.
Among such sheet cooling methods, the method using metal rolls and / or steel belts on both sides of the sheet is the most preferable method because a sheet surface with less surface irregularities, that is, a sheet having excellent transparency can be obtained. It is.

  The polypropylene thermoforming sheet can be used as a multilayer sheet in addition to a single layer. A multilayer sheet is a multilayer sheet in which a gas barrier resin layer, an adhesive resin layer, a recycled resin layer, a candle resin layer, etc. are stacked using an extruder equipped with a plurality of dies and using a feed block and a multi-manifold. Can do.

The thickness of the polypropylene thermoforming sheet is preferably 0.15 to 3 mm, more preferably 0.2 to 2.5 mm, and particularly preferably 0.3 to 2 mm.
If the thickness is significantly less than 0.15 mm, the rigidity is impaired. On the other hand, if the thickness is significantly greater than 3 mm, the transparency may not be sufficient.

The polypropylene thermoforming sheet of the present invention preferably has a tensile modulus of 1000 Mpa or more, more preferably 1200 Mpa or more, and particularly preferably 1400 Mpa or more.
If the tensile elastic modulus is 1000 Mpa or more, the molded product obtained by thermoforming such as vacuum forming method or pressure forming method (deep drawing) has high rigidity. It can use very suitably for the use of.
A tensile elasticity modulus means the average value of the value of MD obtained by the postscript evaluation method, and the value of TD.

In the polypropylene thermoforming sheet of the present invention, HAZE is preferably 15% or less, more preferably 13% or less, and particularly preferably 10% or less.
If HAZE is 15% or less, the molded product obtained by thermoforming such as vacuum forming method or pressure forming method (deep drawing) has high transparency, so that it can be used for pharmaceuticals, industrial products, foods, daily necessities. It can be used very suitably for applications such as packaging containers.

Further, the polypropylene thermoforming sheet of the present invention preferably has a draw-down retention time of 10 seconds or more, more preferably 15 seconds or more, and particularly preferably 20 seconds or more.
When the draw-down holding time is 10 seconds or more, it is substantially unaffected by draw-down during thermoforming such as vacuum forming or pressure forming, improving size and deep drawability, making molding difficult. Even in the corner portion, it is possible to obtain a molded body with high accuracy with little variation in thickness.
The draw-down holding time refers to the holding time in the thermoformability test of the evaluation method described later.

  The polypropylene-based thermoforming sheet of the present invention may be any sheet surface treatment such as corona discharge treatment, flame treatment, plasma treatment, etc., or a lubricant or antifogging agent applied.

III. Deep-drawn molded product The deep-drawn molded product of the present invention can be obtained by a known thermoforming method such as vacuum forming, vacuum-pressure forming, and plug-assisted vacuum-pressure forming. Examples of the heating method in such thermoforming include indirect heating, hot plate heating, and hot roll heating.

The deep drawing in the present invention refers to one having a drawing ratio of 0.5 or more, which is a ratio of the depth of the formed body to the (maximum) width, regardless of whether the shape of the formed body is a square shape or a round shape.
The deep-drawn molded article of the present invention has a drawing ratio of 0.5 or more, preferably 1 or more, more preferably 1.5 or more.
Further, the deep-drawn molded article of the present invention has a minimum thickness ratio of 40% or more, preferably 45% or more, more preferably 50% or more.
The minimum thickness ratio is the ratio of the thinnest portion of the deep-drawn molded product to the average thickness of the polypropylene thermoforming sheet before molding.
A higher drawing ratio and a higher minimum thickness ratio mean that the product is a deep drawing molded article having a good quality as a product.

IV. Use of deep-drawn molded product The polypropylene-based thermoformed sheet of the present invention is excellent in thermoformability, particularly deep drawability, so that the deep-drawn molded product obtained from the thermoformed sheet is rigid and transparent. It has excellent thickness and little uneven thickness, and can be suitably used for packaging containers such as industrial products, foodstuffs and daily necessities, and packaging materials.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, various physical properties of polypropylene-based thermoforming sheets, (deep-drawing) molded bodies, or constituent components thereof were measured and evaluated according to the following evaluation methods. The thing of was used.

1. Evaluation method (1) Melt flow rate (MFR) [unit: g / 10 min]:
The propylene-based resin conforms to JIS K7210: 1999 “Method for testing plastics-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR)”, condition M (230 ° C., 2.16 kg load). Measured in conformity.
(2) Melting point (Tm) and crystallization temperature (Tc):
Using a DSC6200 manufactured by Seiko Instruments Inc., a sample piece made into a sheet is packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. The crystallization temperature (Tc) is obtained as the maximum crystal peak temperature (° C.) when the temperature is lowered to 20 ° C. and crystallized, and then the maximum melting peak when the temperature is increased to 200 ° C. at 10 ° C./min. The melting point (Tm) was determined as the temperature (° C.).
(3) Molecular weight and molecular weight distribution (Mw, Mn, Q value):
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(4) Temperature rising elution fractionation (TREF):
The TREF measurement method is as described in the present specification using the following apparatus.
(I) TREF part TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (ii) Sample injection part Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Iii) Detection unit Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5mm Window shape 2φ x 4mm oval Synthetic sapphire window Measurement temperature: 140 ° C
(Iv) Pump unit Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. (v) Measurement conditions Solvent: o-dichlorobenzene (including 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(5) ME (memory effect):
Polymer that was extruded through an orifice at a temperature of 190 ° C. using a melt indexer manufactured by Takara at 190 ° C. with a load and an extrusion speed of 0.1 g / min. Was quenched in ethanol and calculated as a value obtained by dividing the value of the strand diameter at that time by the orifice diameter. This value correlates with Log (MFR). When this value is large, it indicates that the swell is large and the product appearance is improved when cooled and solidified by a metal roll and / or a metal belt in sheet forming.
(6) mm fraction:
The measurement was carried out by the method described in the present specification using GSX-400 and FT-NMR manufactured by JEOL. The unit is%.
(7) Measurement of ethylene content:
^A calibration curve was prepared using ¹³ C-NMR and measured using IR.
(8) Elongation viscosity:
It was measured by the method described in the present specification.
(9) Composition analysis:
A calibration curve was prepared by chemical analysis according to JIS method and measured by fluorescent X-ray.

(10) Sheet physical properties:
The tensile elastic modulus and HAZE of the polypropylene thermoforming sheet obtained in each of the examples and comparative examples were measured.
Here, the tensile modulus was measured according to JIS K7127, and HAZE was measured according to JIS K7136.
(11) Thermoformability test (Drawdown resistance evaluation):
The polypropylene thermoforming sheet obtained in each of the examples and comparative examples was cut into a 300 mm square size, and the opening was fixed horizontally to a frame having a size of 250 mm × 250 mm. Heat from above and below with a heater heated to 400 ° C. In this state, a phenomenon as shown in FIG. 6 occurs in the polypropylene thermoforming sheet between the sag amount (sag length) and the heating time.
First, the central part of the sheet hangs down by heating. Next, the sagging sheet is lifted, and then sags again, and this time the return phenomenon does not occur.
The amount of sagging that was first drooped above was defined as the “droop amount” (mm), then the amount that was lifted was termed “return amount” (mm), and the time that continued until the sagging amount sagged further by 5 mm from the point of return was “held” Time "(seconds). The smaller the value of “hanging amount”, the smaller the value of “return amount”, and the longer the “holding time”, the more excellent the vacuum forming and pressure forming properties.

(12) Drawing ratio (deep drawing property):
Using the polypropylene-based thermoforming sheet obtained in each of the Examples and Comparative Examples, the heater temperature was measured in a vacuum / pressure forming machine having a box-shaped cavity having a width of 20 cm, a length of 20 cm, and a depth of 5 to 60 cm (variable). A box-shaped molded body is manufactured by vacuum forming at 400 ° C. At this time, the maximum depth at which the molded body was not torn during molding was determined by changing the depth (cm), and the maximum depth / (maximum) width was defined as the draw ratio (deep drawability). The larger this value, the better the deep drawability.
(13) Molded body appearance:
In the above-described deep drawability evaluation, a molded article having a depth of 20 cm (drawing ratio is 1.0) was used, and the appearance was judged according to the following criteria.
○: A molded article having excellent surface gloss and little change in thickness.
Δ: A molded article having excellent surface gloss but a thin corner.
X: A molded body in which the corner portion is thin and a rugged foreign matter is generated on the surface.

(14) Minimum thickness ratio:
In the evaluation of the average thickness (A) of the polypropylene-based thermoforming sheet before molding and the deep drawability evaluation, the thickness of the molded product having a depth of 20 cm (drawing ratio is 1.0) was measured with a micrometer. After calculating the thinnest part (B), the ratio (B) / (A) was determined as the minimum thickness ratio.
Moreover, the thickness of the bottom corner part of the said molded object was measured with the micrometer.

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

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

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

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

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

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

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

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

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

(2) [Catalyst Synthesis Example 1]
(2-1) Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the above-mentioned cake solid was added, and further 522 g of distilled water was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(2-2) Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (65 mL) was added to form a slurry, to which was added a triisobutylaluminum (25 mmol: heptane solution having a concentration of 143 mg / mL). 6 mL) and stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-t-butylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (30 mL) (solution 1), and further, the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (45 μmol) prepared in Example 2 was dissolved in toluene (12 mL) (Solution 2 ).

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

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

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

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

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

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

(2) [Catalyst synthesis example 3]:
(2-1) Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1500 g) was added to 2260 g of distilled water, and then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 480 minutes. The reaction slurry was cooled to room temperature in 1 hour and washed to pH 3 with distilled water. The resulting solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further dried at 215 ° C. under a nitrogen stream under a rotary kiln condition for 295 g of chemically treated smectite. Got.
The composition of the chemically treated smectite is Al: 2.72% by weight, Si: 43.48% by weight, Mg: 0.36% by weight, Fe: 0.61% by weight, and Al / Si = 0.065 [ mol / mol].

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

(3-3) Propylene polymerization:
Polymerization Example 1 except that 20 g of the prepolymerized catalyst 3 synthesized above was used instead of the prepolymerized catalyst 1 in a weight excluding the prepolymerized polymer and the polymerization temperature was set to 70 ° C. for 3 hours without adding hydrogen. The same polymerization was carried out to obtain 6.9 kg of polymer (PP-4). The catalytic activity was 345 (g-PP / g-cat). In particular, since this polymer has low catalytic activity, the amount of catalyst residue in the polymer is large, and there is a concern that the hue deteriorates during molding.

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

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

(D) Crystal nucleating agent Adeka Stab NA21 manufactured by Adeka Co., Ltd .: Bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2 , 3] dioxaphosphocin-6-oxide) a complex of an aluminum hydroxide salt and an organic compound.

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

The above-mentioned pellets are put into an extruder having a screw diameter of 40 mm, a sheet cast by heat melting and plasticizing at a resin temperature of 230 ° C. and extruded from a T-die is a mirror-finished metal cast roll whose surface temperature is controlled at 60 ° C. Was taken up at a speed of 1 m / min while being cooled and solidified to obtain a polypropylene thermoforming sheet having a width of 500 mm and a thickness of 0.5 mm.
The various evaluations described above were performed on this sheet. The results are shown in Table 1.
The propylene-based thermoforming sheet that satisfies the configuration of the present invention has high rigidity, a small HAZE value, excellent thermoformability such as draw-down resistance, and a molded product with little uneven thickness even with deep drawing. It was.

[Example 2]
It implemented like Example 1 except having used the polymer (PP-2) instead of the polymer (PP-1). The evaluation results are shown in Table 1.
The propylene-based thermoforming sheet that satisfies the constitution of the present invention has a high rigidity, a small HAZE value, excellent thermoformability such as draw-down resistance, and a smooth molded article with little unevenness even at a deep draw. was gotten.

[Example 3]
It implemented similarly to Example 1 except having used the polymer (PP-3) instead of the polymer (PP-1). The evaluation results are shown in Table 1.
The propylene-based thermoforming sheet satisfying the configuration of the present invention has high rigidity, a small HAZE value, excellent thermoformability such as draw-down resistance, and a smooth appearance with little uneven thickness even at a deep drawing. A shaped body was obtained.

[Example 4]
Instead of the propylene-based resin (PP-1), a polymer mixture obtained by blending 70% by weight of the propylene-based resin (PP-1) and 30% by weight of the propylene-based resin (Y: WEG7T) was used. The same procedure as in Example 1 was performed. The evaluation results are shown in Table 1.
The propylene-based thermoforming sheet that satisfies the configuration of the present invention has high rigidity, a small HAZE value, excellent thermoformability such as draw-down resistance, and a smooth appearance with little unevenness even in deep drawing. A molded product was obtained.

[Example 5]
Example except that a polymer mixture obtained by blending 20% by weight of polymer (PP-1) and 80% by weight of propylene resin (Y: WEG7T) was used instead of polymer (PP-1). As in 1. The evaluation results are shown in Table 1.
The propylene-based thermoforming sheet satisfying the configuration of the present invention has high rigidity, particularly a low HAZE value, excellent thermoformability such as draw-down resistance, and a smooth appearance with little unevenness even at deep drawing. A molded product was obtained.

[Comparative Example 1]
It implemented like Example 1 except having used propylene type resin (PP-4) different from propylene type polymer (X) specified in the present invention instead of polymer (PP-1). The evaluation results are shown in Table 2.
The propylene-based thermoforming sheet that does not satisfy the configuration of the present invention is inferior in draw-down resistance, has a large thickness deviation in the case of deep drawing, and a satisfactory molded product cannot be obtained.

[Comparative Example 2]
It implemented similarly to Example 1 using the electron beam irradiation bridge | crosslinking type propylene resin (PF814) different from the propylene polymer (X) specified in this invention instead of the polymer (PP-1). . The evaluation results are shown in Table 2.
The propylene-based thermoforming sheet that does not satisfy the configuration of the present invention has a large HAZE value and is excellent in resistance to drawdown, but in the case of deep drawing, the uneven thickness is large, fluffing occurs and the surface is rough, A satisfactory molded product could not be obtained.

[Comparative Example 3]
It implemented like Example 1 except having used the propylene polymer (Y: WEG7T) different from the propylene-type polymer (X) specified in this invention instead of the polymer (PP-1). The evaluation results are shown in Table 2.
The propylene-based thermoforming sheet that does not satisfy the constitution of the present invention has a small HAZE value, but is inferior in draw-down resistance, has a large uneven thickness in the case of deep drawing, and a satisfactory molded product was not obtained.

  Since the polypropylene-based thermoforming sheet of the present invention is excellent in thermoformability, particularly deep drawability, the deep-drawn molded product obtained from the thermoforming sheet is used for packaging industrial products, foodstuffs, daily necessities and the like. It can be suitably used for containers, packing materials, etc., and has high industrial applicability.

Claims (9)

Propylene resin containing a polymer mixture of propylene polymer (X) 3 to 100% by weight and propylene polymer (Y) 0 to 97% by weight satisfying the requirements specified in the following (i) to (vi) A polypropylene thermoforming sheet obtained from the composition.
(I) Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 0.2 to 20 g / 10 min.
(Ii) The ratio (Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 to 10.5.
(Iii) In the molecular weight distribution curve obtained by GPC, the ratio of the component having a molecular weight (M) of 2 million or more to the total amount is 0.4% by weight or more and less than 10% by weight.
(Iv) In temperature rising elution fractionation (TREF) with orthodichlorobenzene (ODCB), the component eluted at a temperature of 40 ° C. or less is 3.0% by weight or less.
(V) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.
(Vi) The strain hardening degree (λmax) in the measurement of the extensional viscosity is 6.0 or more.   The polypropylene-based thermoforming sheet according to claim 1, wherein the propylene-based resin composition contains 0.01 to 1 part by weight of a crystal nucleating agent with respect to 100 parts by weight of the polymer mixture. The polypropylene-based thermoforming sheet according to claim 1 or 2, wherein the propylene-based polymer (X) further satisfies the following requirement (vii).
(Vii) (ME) ≧ −0.26 × log (MFR) +1.9
[In the formula, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and a diameter of 1.00 mmφ, sets the temperature in the cylinder to 190 ° C., applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate is divided by the orifice diameter. ] The polypropylene-based thermoforming sheet according to any one of claims 1 to 3, wherein the propylene-based polymer (X) further satisfies the following requirement (viii).
(Viii) In the molecular weight distribution curve obtained by GPC, the common logarithm of the molecular weight corresponding to the peak position is Tp, and the common logarithm of the molecular weight at the position where it is 50% of the peak height is L ₅₀ and H ₅₀ (L ₅₀ is Tp Lower molecular weight side, H ₅₀ is higher molecular weight side than Tp), and α and β are defined as α = H ₅₀ −Tp and β = Tp−L ₅₀ , respectively, α / β is larger than 0.9 and 2 Less than 0.0. The propylene polymer (Y) is polymerized using a metallocene catalyst, and satisfies the following characteristics (i) to (iv): 5. Polypropylene thermoforming sheet.
(I) MFR (230 ° C., 2.16 kg load) is 0.5 to 20 g / 10 min.
(Ii) The melting peak temperature (Tm) measured by the DSC method is 120 to 165 ° C.
(Iii) The molecular weight distribution (Q value: Mw / Mn) measured by the GPC method is 1.5 to 4.5.
(Iv) In the elution curve obtained by temperature rising elution fractionation (TREF), the difference (T ₈₀ -T ₂₀ ) between the temperature (T ₂₀ ) extracted at 20 wt% and the temperature (T ₈₀ ) extracted at 80 wt% It is 10 degrees C or less.   The said polymer mixture consists of propylene polymer (X) 5 to 90 weight% and propylene polymer (Y) 10 to 95 weight%, The any one of Claims 1-5 characterized by the above-mentioned. The sheet for polypropylene thermoforming as described in 1.   The polypropylene-based heat according to any one of claims 1 to 6, wherein the tensile elastic modulus is 1000 Mpa or more, HAZE is 15% or less, and the draw-down holding time is 10 seconds or more. Sheet for molding.   The crystal nucleating agent is at least one selected from the group consisting of aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, amide nucleating agents, and rosin metal salts. The polypropylene thermoforming sheet according to claim 2.   A deep-drawn molded article obtained by thermoforming the polypropylene-based thermoforming sheet according to any one of claims 1 to 8 and having a drawing ratio of 0.5 or more and a minimum thickness ratio of 40% or more. .

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