JP6217300B2 - RESIN COMPOSITION FOR SHEET MOLDING, RESIN SHEET USING THE SAME, AND PACKAGE FOR HEAT TREATMENT - Google Patents

Description

  The present invention relates to a resin composition for sheet molding, a resin sheet using the same, and a package for heat treatment. Specifically, even if heat treatment under pressure such as pressurized steam treatment or pressurized hot water treatment is performed. A resin composition for a sheet which is not easily deformed, has excellent heat resistance, has good transparency, flexibility, impact resistance, secondary processing suitability, and also has good moldability, and The present invention relates to a propylene-based resin sheet and a heat treatment package.

The performance required for packaging bags that need to be sterilized and sterilized, such as retort packagings and infusion bags for chemicals, etc. Flexibility to enable liquid use, low temperature impact resistance to prevent bag breakage even when handled in extremely cold regions (such as -20 ° C), deformation and fusion even at 121 ° C sterilization and sterilization For example, heat resistance for preventing heat treatment, and suitability for secondary processing such as heat sealing characteristics for easy bag-making.
Especially for infusion bags, vinyl chloride resin was used as a material that satisfies the above-mentioned performance. However, there are problems such as elution of plasticizers, difficulty in disposal, and consideration for the global environment in recent years. For this reason, it has been replaced by polyolefin resin.

  Although the infusion bag mainly composed of polyethylene is excellent in flexibility and impact resistance, it has poor heat resistance, and an appearance defect such as deformation occurs at a sterilization temperature of 121 ° C. which is an overkill condition, and performance as an infusion bag. Cannot be satisfied (see, for example, Patent Document 1). On the other hand, an infusion bag mainly composed of polypropylene has good heat resistance, but it is hard as an infusion bag material and lacks impact resistance at low temperatures. (For example, refer to Patent Document 2).

  Therefore, a technique in which an elastomer component is added to polypropylene to impart flexibility and impact resistance is disclosed (for example, see Patent Document 3). However, there is a problem that the heat resistance of polypropylene is sacrificed, and low molecular weight components after sterilization are bleed out and transparency is deteriorated. There is also a disclosure of a technique of adding a styrene elastomer as an elastomer component (see, for example, Patent Document 4), but blocking is likely to occur and it is difficult to say that the productivity is excellent. The cost is higher than that of an elastomer, and there remains a problem in terms of cost.

Separately, a polypropylene block copolymer has been developed in which an elastomer component is added by continuous polymerization using a Ziegler-Natta catalyst (see, for example, Patent Document 5), but bleedout after sterilization still occurs. The transparency is not good. On the other hand, a water-cooled inflation film (for example, see Patent Document 6) composed of a propylene-ethylene block copolymer in which an elastomer component is added by continuous polymerization using a metallocene catalyst has been proposed. Although the bleed out has been improved, the impact resistance at low temperatures is still insufficient. Moreover, although the medical film containing a heterogeneous blend (for example, refer patent document 7) is proposed, the impact resistance in low temperature was inadequate.
As described above, there is a demand for a transfusion bag material that has a sufficient balance of heat resistance, transparency, flexibility, and impact resistance, and that is low in cost, but the current situation is that no satisfactory material has been found. It was.

  The infusion bag making process includes a process of fusing with spouts, injection parts such as a discharge port and an injection port, etc., and it is necessary to melt the film for sufficient fusing. For this reason, extremely severe (high temperature, high pressure, long time, etc.) heat sealing is performed. In a sufficiently melted state, the molten resin sticks to the seal bar, and the productivity cannot be denied. Thus, a technique is disclosed in which the inner layer is melted while the outer layer remains solid by providing a melting point difference between the outer layer and the inner layer by stacking (see, for example, Patent Document 7). However, since the inner layer is a polyethylene-based resin, it can withstand a sterilization temperature of 115 ° C., but the 121 ° C. sterilization causes the inner surfaces of the films to be fused together, and the heat resistance is not sufficient.

  Furthermore, Patent Document 8 proposes a sheet having excellent transparency, flexibility, heat resistance, and impact resistance (drop bag impact). However, the impact resistance at extremely low temperatures (for example, −20 ° C.) is insufficient, and the sheet may be destroyed during transportation in a cold region.

  Disclosed is a technique (see Patent Document 9) that makes it possible to impart impact resistance and suitability for bag-making processes under cryogenic temperatures, specifically the shape of the heat-sealed part after bag-making, which is the above-mentioned problem. Yes. However, although the shape retention temperature at which large deformation of the heat seal portion is suppressed is improved, deformation at a temperature lower than the shape retention temperature has occurred, and there is still room for improvement of the shape retention rate. Further, the composition described in Patent Document 9 has insufficient sheet molding stability. For example, in order to eliminate sheet surface roughness and suppress anisotropy of physical properties, the lip width is wide or the blow ratio is small. When molding is performed by a molding machine, there is a problem that the thickness variation of the sheet is large and a good sheet cannot be obtained.

JP-A-9-308682 JP-A-9-99036 JP-A-9-75444 JP-A-9-324022 JP 2006-307072 A Special table 2008-524391 JP 2007-245490 A JP 2010-138211 A JP 2012-82405 A

Propylene (co) polymer that exhibits heat resistance in order to have a balance of transparency, heat resistance, flexibility, impact resistance, suitability for secondary processing, and sheet formability, which are the performance required for packaging bags for heat treatment. It is effective to use a combination of a propylene-α-olefin random copolymer added with a specific amount of α-olefin that can be softened without impairing transparency. On the other hand, as it is, it can not withstand severe heat seal conditions, the thickness of the heat seal part becomes thin, and when the heat treatment package is dropped with the contents in place, cracks enter from the heat seal wrinkles, There is a possibility of breaking the bag. Further, in a molding machine having a wide lip width or a small blow ratio, there is a possibility that an elongation flow instability phenomenon called draw resonance may occur.
Therefore, the object of the present invention is to solve the above-mentioned problems, and is excellent in flexibility, transparency, heat resistance, impact resistance, particularly impact resistance at extremely low temperatures (for example, −20 ° C.), and An object of the present invention is to provide a resin composition for a sheet that can withstand severe heat-sealing conditions at the time of bag making and that is excellent in sheet moldability, and a package for heat treatment using the same.

As a result of conducting various studies and analyzes to solve the above problems, the present inventors have identified a specific mixture having a specific propylene-α-olefin copolymer, a specific modifier, and a branched structure. It was found that the above-mentioned problems can be solved in a well-balanced manner by blending a specific amount of each of these polypropylene resins, and the present inventors have obtained the knowledge that a sheet that can solve the above-mentioned problems can be obtained by the above resin composition. It was.
The present invention provides the following sheet-forming resin composition, propylene-based resin sheet, and heat treatment package.

[1] Propylene resin composition (A) 1 to 98 wt% satisfying the following (Ai) to (A-ii), modifier (B) 1 to 50 wt% satisfying the following (Bi), and Sheet molding resin comprising a propylene-based resin composition (X) containing 1 to 50 wt% (provided that A + B + C = 100 wt%) of a polypropylene resin (C) having a branched structure satisfying (Ci) Composition.
Propylene resin composition (A):
(Ai) The propylene-based resin composition (A) has a melting peak temperature (Tm (A1)) of 120 to 170 ° C., a propylene (co) polymer component (A1) of 30 to 70 wt%, and an α-olefin content. (E [A2]) contains 70-30 wt% of propylene-α-olefin random polymer component (A2) of 7-30 wt%.
(A-ii) Melt flow rate (MFR (A): 230 ° C., 2.16 kg) is in the range of 0.5 to 20 g / 10 min.
・ Modifier (B):
(Bi) At least one modifier selected from the group consisting of an ethylene-α-olefin copolymer and a styrene elastomer.
-Propylene resin (C) having a branched structure:
(Ci) Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7, or MT ≧ 15
Satisfy one of the following.

[2] A propylene-based resin sheet comprising at least one layer formed of the resin composition for sheet molding described in [1].
[3] The propylene-based resin sheet according to [2], wherein the thickness is 0.01 mm to 1.0 mm.
[4] A heat treatment package using the propylene-based resin sheet according to [2] or [3].
[5] The package for heat treatment as described in [4] above, wherein the package for heat treatment is an infusion bag.

The basic requirements for the resin composition for sheet molding of the present invention, the propylene resin sheet using the same, and the package for heat treatment are at least one specific propylene resin composition (A) and specific modifier (B) The propylene resin composition (A) used for the propylene resin composition (X) is to use the propylene resin composition (X) containing the polypropylene resin (C) having a specific branched structure. Contains a propylene (co) polymer component (A1) having a melting peak temperature in a specific range and a propylene-α-olefin random copolymer (A2) having a specific α-olefin content, , Transparency and flexibility are high, and transparency and flexibility can be imparted to the resulting sheet.
The modifier (B) used for the propylene resin composition (X) is at least one or more modifiers selected from the group consisting of an ethylene-α-olefin copolymer and a styrene elastomer, and the resulting sheet Excellent flexibility and low-temperature impact resistance.
The polypropylene resin (C) having a branched structure used for the propylene-based resin composition (X) is specified by melt tension, and imparts good secondary processability and sheet formability to the obtained sheet. be able to.

  Therefore, the propylene-based resin sheet of the present invention and the heat-treated packaging body using the sheet are excellent in sheet formability in addition to transparency, flexibility, low-temperature impact resistance, and secondary processing suitability. It can be particularly suitably used for applications such as packaging and infusion bags.

It is a graph which shows the temperature-loss tangent (tan-delta) curve obtained by the solid-viscoelasticity measurement (DMA) of the water-cooled inflation sheet of the propylene-type resin composition (A-1) obtained by manufacture example (A-1). Yes, an example where a single peak has 0 ° C. or lower is shown.

The resin composition for sheet molding of the present invention is a propylene-based resin composition (A) satisfying the above (Ai) to (A-ii) (A) 1 to 98 wt%, a modifier satisfying the above (Bi) ( B) A propylene-based resin composition (X) containing 1 to 50 wt% and a polypropylene resin (C) having a branched structure satisfying the above (C-i) (C) 1 to 50 wt% (A + B + C = 100 wt%) It is characterized by.
The propylene-based resin sheet of the present invention includes at least one layer composed of the above-mentioned sheet-forming resin composition, and the heat-treatment packaging body of the present invention uses this propylene-based resin sheet. It is characterized by that.
Hereinafter, each component of the propylene-based resin composition (X) of the present invention, production of each component, propylene-based resin sheet, and heat treatment package will be described in detail.

<Main layer (1) Propylene resin composition (X)>
The propylene-based resin composition (A), the modifier (B), and the polypropylene resin (C) having a branched structure constituting the propylene-based resin composition (X) used for the main layer of the propylene-based resin sheet will be described below. .

(1) Propylene resin composition (A)
-Properties of the propylene-based resin composition (A) The propylene-based resin composition (A) (hereinafter sometimes referred to as component (A)) used as one component of the propylene-based resin composition (X) is transparent. It needs to be highly flexible. In order to satisfy these requirements at a high level, the component (A) needs to satisfy the following conditions (A-i) to (A-ii).

-Basic rules of component (A) Component (A) is a propylene-based resin composition (A) that satisfies the following conditions (Ai) to (A-ii).
(A-i):
30-70 wt% of propylene (co) polymer component (A1) having a melting peak temperature (Tm (A1)) of 120 to 170 ° C., α-olefin content of 2 or 4 to 8 carbon atoms (α [A2]) Contains 70-30 wt% of propylene-α-olefin random copolymer (A2) of 7 wt% or more and less than 30 wt%.
(A-ii):
The melt flow rate (MFR (A): 230 ° C., 2.16 kg) is in the range of 0.5 to 20 g / 10 minutes.

Melting peak temperature of propylene (co) polymer component (A1) (Tm (A1))
A component (A1) is a component which determines crystallinity in a propylene-type resin composition (component (A)). In order to improve the heat resistance of the component (A), the melting peak temperature Tm (A1) of the component (A1) (hereinafter sometimes referred to as Tm (A1)) needs to be high, but Tm ( When A1) is too high, flexibility and transparency are hindered. Moreover, when Tm (A1) is too low, heat resistance will deteriorate and thinning will advance at the time of heat sealing. Tm (A1) needs to be in the range of 120 to 170 ° C.

  The melting peak temperature Tm here is a value obtained with a differential scanning calorimeter (DSC manufactured by TA Instruments). Specifically, a sample amount of 5.0 mg is taken and held at 200 ° C. for 5 minutes. It is a value obtained as a melting peak temperature when crystallization is performed at a temperature lowering speed of 10 ° C./min up to ° C. and further melted at a temperature rising speed of 10 ° C./min.

-Ratio of component (A1) in component (A) Ratio W (A1) of component (A1) in component (A) is a component that imparts heat resistance to component (A). When there is too much A1), flexibility, transparency and impact resistance cannot be sufficiently exhibited. Therefore, the ratio of the component (A1) needs to be 70 wt% or less.
On the other hand, if the proportion of the component (A1) is too small, the heat resistance is lowered even if the Tm (A1) is sufficient, and there is a risk of deformation in the sterilization and sterilization processes. Therefore, the proportion of the component (A1) Must be 30 wt% or more.

-Α-olefin content α [A2] in the propylene-α-olefin random copolymer (A2)
The component (A2) is a component necessary for improving the flexibility, impact resistance and transparency of the component (A), and is preferably obtained using a metallocene catalyst. Generally, in the propylene-α-olefin random copolymer, the increase in the α-olefin content decreases the crystallinity and increases the flexibility improving effect. Therefore, the α-olefin content in the component (A2) α [A2] (hereinafter also referred to as α [A2]) needs to be 7 wt% or more.
On the other hand, if α [A2] is excessively increased in order to reduce the crystallinity of component (A2), the transparency is lowered. Therefore, α [A2] of the component (A2) in the component (A) used in the present invention needs to be 30 wt% or less.

  The α-olefin as a comonomer used for the component (A1) and the component (A2) is preferably an α-olefin having 2 or 4 to 20 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene. .Alpha.-olefins other than propylene such as 3-methyl-1-butene and 4-methyl 1-pentene, and vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane and vinylnorbornane. Two or more of these comonomers may be copolymerized. The comonomer is preferably ethylene and / or 1-butene.

-Ratio of the component (A2) in the component (A) The ratio W (A2) of the component (A2) in the component (A) is too low. % Or less is necessary.
On the other hand, if W (A2) becomes too small, the effect of improving the flexibility and impact resistance cannot be obtained, so W (A2) needs to be 30 wt% or more.

Here, W (A1) and W (A2) are values obtained by temperature rising elution fractionation (TREF), and α-olefin contents α [A1] and α [A2] are values obtained by NMR. is there.
Specifically, the following method is used.

・ Identification of W (A1) and W (A2) by temperature-temperature elution fractionation (TREF) Method for evaluating crystallinity distribution of propylene-α-olefin random copolymer by temperature-temperature elution fractionation (TREF) Is well known to those skilled in the art. For example, detailed measurement methods are shown in the following documents.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)

  Component (A) used in the present invention has a large difference in crystallinity between component (A1) and component (A2), and when both components are produced using a metallocene-based catalyst, Since the distribution is narrow, there are very few intermediate components between the two, and both can be accurately separated by TREF.

In the present invention, the TREF measurement is specifically performed as follows.
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, a component of −15 ° C. o-dichlorobenzene (containing 0.5 mg / ml BHT), which is a solvent, flows through the column at a flow rate of 1 ml / min, and is dissolved in o-dichlorobenzene at −15 ° C. in the TREF column. Is eluted for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

In the obtained elution curve, component (A1) and component (A2) show their elution peaks at the respective temperatures T (A1) and T (A2) due to the difference in crystallinity, and the difference is sufficiently large. Separation is possible at an intermediate temperature T (A3) (= {T (A1) + T (A2)} / 2).
Here, if the integrated amount of the component eluted before T (A3) is defined as W (A2) wt%, and the integrated amount of the component eluted at T (A3) or higher is defined as W (A1) wt%, W (A2) Corresponds to the amount of the component (A2), and the integrated amount W (A1) of the component eluted at T (A3) or higher corresponds to the amount of the component (A1) having relatively high crystallinity.

The equipment and specifications used for the measurement are shown below.
(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 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 (sample injection part)
Injection method: Loop injection method Injection volume: Loop size 0.1ml
Inlet heating method: Aluminum heat block measurement temperature: 140 ° C

(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR micro flow cell Optical path length 1.5mm
Window shape 2φ × 4mm long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT)
Sample concentration: 5 mg / ml
Sample injection volume: 0.1 ml
Solvent flow: 1 ml / min

・ Specification of α [A1] and α [A2] The α-olefin (preferably ethylene) content α [A1] and α [A2] of each component is determined by a temperature rising column fractionation method using a preparative fractionator. Each component is separated, and the α-olefin (preferably ethylene) content of each component is determined by NMR.
The temperature rising column fractionation method is a measurement method disclosed in, for example, Macromolecules 21 314-319 (1988).
Specifically, the following method was used in the present invention.

-Temperature rising column fractionation A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 ml of a sample o-dichlorobenzene solution (10 mg / ml) dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (A3) (obtained for TREF measurement) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (A3), 800 ml of o-dichlorobenzene of T (A3) is allowed to flow at a flow rate of 20 ml / min, whereby components soluble in T (A3) present in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 ml of o-dichlorobenzene as a solvent at 140 ° C. is flowed at a flow rate of 20 ml / min. , T (A3) is eluted and recovered.
The polymer-containing solution obtained by fractionation is concentrated to 20 ml using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is collected by filtration and dried overnight in a vacuum dryer.

· ^{13 C-NMR} according to the ethylene content Measurement of fractionated by resulting component of α- olefin (preferably ethylene) content of alpha [A2] were measured under the following conditions by complete proton decoupling method, ¹³ C -Determined by analyzing NMR spectra.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / ml
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more

Spectral assignment may be performed with reference to Macromolecules 17 1950 (1984), for example. The attribution of spectra measured under the above conditions is as shown in Table 1. In the table, symbols such as S _αα represent Carman et al. (Macromolecules 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. . As described in Macromolecules 15 1150 (1982) and the like, the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.
Therefore, [PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100

  The propylene-α-olefin random copolymer contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the minute peaks shown in Table 2. .

In order to obtain an accurate α-olefin (ethylene) content, it is necessary to include the peaks derived from these different bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from the different bonds, Further, since the amount of heterogeneous bonds is small, the ethylene content of the present invention is the same as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain heterogeneous bonds (1) to (7). It is determined using the relational expression.
The conversion of the ethylene content from mol% to wt% is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
(Here, X is the ethylene content in mol%.)

-Producing method of propylene-based resin composition (A) As a preferred producing method of component (A) used in the present invention, a melting peak temperature Tm (A1) in DSC measurement in the first step is determined using a metallocene catalyst. 30 to 70 wt% of propylene (co) polymer component (A1) in the range of 120 to 170 ° C., and propylene-α- in which the α-olefin content α [A2] is 7 wt% or more and 30 wt% or less in the second step. It can be obtained by sequentially polymerizing 70-30 wt% of the olefin random copolymer component (A2). A specific method for polymerizing the component (A1) in the first step and sequentially polymerizing the component (A2) in the second step using a metallocene-based catalyst uses, for example, the method described in JP-A-2005-132979. It is assumed that the entire contents of the publication are incorporated herein by reference.

  Moreover, even if a component (A) is not a sequential polymerization product, the propylene-α-olefin copolymer (A1) satisfying the melting peak temperature Tm (A1) and the α-olefin content α [A2] are satisfied. A blend of a propylene-α-olefin random copolymer (A2) may be used.

(A-ii) Melt flow rate MFR of component (A) (A)
The melt flow rate MFR (230 ° C., 2.16 kg) (hereinafter sometimes referred to as MFR (A)) of the component (A) used in the present invention is in the range of 0.5 to 20 g / 10 minutes. is necessary.
MFR (A) is determined by the ratio of each MFR corresponding to component (A1) and component (A2) (hereinafter also referred to as MFR (A1) and MFR (A2)). If MFR (A) is in the range of 0.5 to 20 g / 10 min, MFR (A1) and MFR (A2) are optional as long as the object of the present invention is not impaired. However, when the MFR difference between the two is greatly different, there is a risk of appearance failure or the like. Therefore, both MFR (A1) and MFR (A2) are preferably in the range of 0.5 to 20 g / 10 minutes. .

If the MFR (A) is too low, the resistance to rotation of the molding machine screw increases, so that not only the motor load and the tip pressure increase, but also the problem arises that the appearance of the sheet deteriorates due to the rough surface of the sheet. Therefore, MFR (A) is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more.
On the other hand, if the MFR (A) is too high, the molding tends to be unstable and it is difficult to obtain a uniform sheet. Therefore, the MFR is preferably 20 g / 10 min or less, more preferably 10 g / 10 minutes or less.
Here, MFR is a value measured according to JIS K7210.
The melt flow rate (MFR) can be easily adjusted by adjusting the temperature and pressure, which are polymerization conditions, in the sequential polymerization, or by controlling the amount of hydrogen added during the polymerization of a chain transfer agent such as hydrogen. Adjustments can be made.

Moreover, it is preferable that a component (A) has the following characteristic (A-iii).
(A-iii) A temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) measured with a 200 μm-thick sheet molded by a water-cooled inflation method is observed in the range of −60 ° C. to 20 ° C. The peak of the tan δ curve representing the glass transition should be a single peak below 0 ° C.

When the component (A) has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) and the glass transition temperature of the amorphous part contained in the component (A2) are different from each other. , Not single. In this case, there arises a problem that transparency as a sheet is likely to deteriorate.
Depending on the apparatus used for the measurement and the flexibility of the sample, the 200 μm-thick sheet may be insufficiently detected for stress and may be difficult to measure. In such a case, the measurement may be performed by stacking a plurality of sheets, for example, by stacking two sheets, and the same result can be obtained by measuring by the method.

Here, the solid viscoelasticity measurement (DMA) is specifically performed by applying a sine distortion of a specific frequency to a strip-shaped sample piece and detecting the generated stress. The frequency is 1 Hz, and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. The peak of the tan δ curve at 0 ° C. or lower generally observes the glass transition of the amorphous part, and in the present invention, this peak temperature is the glass transition temperature Tg. Defined as (° C).
In addition, the manufacturing conditions of the sheet | seat of 200 micrometers thickness by a water cooling inflation method are performed by the method detailed in the below-mentioned Example. However, in the method described later, the raw material charged into each extruder is only the propylene-based resin composition (A).

-Control method of component of propylene-based resin composition (A) Each element of propylene-based resin composition (A) used in the present invention is controlled as follows and is necessary for propylene-based resin composition (A) It can be manufactured to meet the required configuration requirements.
The melting peak temperature (Tm (A1)) of the component (A1) can be controlled by appropriately adjusting the amount ratio of propylene and α-olefin supplied to the polymerization tank. In order to control the melting peak temperature (Tm (A1)) to, for example, 120 ° C. to 170 ° C., the α-olefin content (α [A1]) is almost 0, depending on the type of catalyst used. The component (A1) having a desired melting peak temperature (Tm (A1)) can be produced by adjusting in a range of about 10 to 10% by weight.
Further, in order to control the α-olefin content (α [A2]) of the component (A2) within a predetermined range, in the case of sequential polymerization, the propylene and α-olefin supplied to the polymerization tank in the second step The quantity ratio may be adjusted as appropriate. When the metallocene catalyst is used, the relationship between the supply ratio and the α-olefin content in the resulting propylene α-olefin random copolymer varies depending on the type, but the required α-olefin content (α The component (A2) having [A2]) can be produced.

In the case of sequential polymerization, the amount W (A1) of the component (A1) and the amount W (A2) of the component (A2) are the same as the production amount of the first step for producing the component (A1) and the component ( It can be controlled by changing the ratio of the production amount of A2).
Adjustment of the melt flow rate of a component (A) is as having mentioned above.

-Proportion of component (A) in propylene-based resin composition (X) The proportion of the propylene-based resin composition (component (A)) in the main layer structure is component (A), component (B), and component (C). It is necessary to be in the range of 1 to 98 wt% with respect to the total amount of 100 wt%.
When the content of the component (A) is too small, good flexibility and transparency cannot be obtained. On the other hand, if the content of the component (A) is too large, impact resistance at low temperatures tends to decrease.

(2) Reformer (B)
-Property of component (B) The modifier (B) (hereinafter also referred to as component (B)) used as one component of the propylene-based resin composition (X) of the propylene-based resin sheet of the present invention is as follows. It is necessary to be at least one type of modifying material selected from the group consisting of an ethylene-α-olefin copolymer and a styrene elastomer. Component (B) is a component that functions to improve the impact resistance and flexibility of the propylene-based resin composition (X).

  The ethylene-α-olefin copolymer is a copolymer obtained by copolymerizing ethylene and preferably an α-olefin having 3 to 20 carbon atoms, and the α-olefin is a copolymer having 3 to 20 carbon atoms. For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene and the like can be preferably exemplified, and commercially available products include trade name affinity (AFFINITY) and engage (ENGAGE) manufactured by DuPont Dow. ), Trade name kernel (KERNEL) manufactured by Nippon Polyethylene Co., Ltd., trade name Exact (EXACT) manufactured by ExxonMobil.

  A styrene-type elastomer can be used selecting it suitably from what is marketed. For example, as a hydrogenated product of a styrene-butadiene block copolymer, “Clayton G” from Clayton Polymer Japan Co., Ltd. and “Tuftec” from Asahi Kasei Kogyo Co., Ltd. As a hydrogenated product, Kuraray Co., Ltd. has a product name of “Septon”. As a hydrogenated product of a styrene-vinylated polyisoprene block copolymer, Kuraray Co., Ltd. has a product name of “Hibler”. A polymer hydrogenated product is sold under the trade name “Dynalon” by JSR Corporation, and is appropriately selected from these product groups.

Component (B) Method for Producing Ethylene-α-Olefin Copolymer Component (B) used in the present invention preferably has a low density from the viewpoint of transparency, and further suppresses stickiness and bleed out. For this purpose, it is desirable that the distribution of crystallinity and molecular weight is narrow. Therefore, it is desirable to use a metallocene catalyst capable of narrowing crystallinity and molecular weight distribution for the production of component (B).
The metallocene catalyst and the polymerization method using the same will be described below.

-Metallocene catalyst As the metallocene catalyst, various known catalysts used for the polymerization of ethylene-α-olefin copolymers can be used. Specific examples include metallocene catalysts described in JP-A-58-19309, JP-A-59-95292, JP-A-60-35006, and JP-A-3-16388. .

・ Polymerization method Specific polymerization methods include a slurry method, a gas phase fluidized bed method and a solution method in the presence of these catalysts, or a high-pressure bulk at a pressure of 200 kg / cm ² or more and a polymerization temperature of 100 ° C. or more. Examples thereof include a polymerization method. A preferable production method includes high-pressure bulk polymerization.

-Proportion of component (B) in propylene-based resin composition (X) The proportion of component (B) in propylene-based resin composition (X) is that of component (A), component (B), and component (C). It is necessary to be in the range of 1 to 50 wt% with respect to the total amount of 100 wt%. When the content of the component (B) is less than 1 wt%, the low temperature impact resistance is not sufficiently imparted. On the other hand, when the content of the component (B) is too large, the heat resistance is deteriorated and the thickness of the sheet is likely to be uneven, and a sheet having a good appearance cannot be obtained.

(3) Polypropylene resin having branched structure (C)
-Property of component (C) By adding the polypropylene resin (C) which has the following branched structure to the propylene-type resin composition (X) of this invention, a moldability and thinning suppression can be expressed. .
The component (A) used as the main component of the propylene-based resin composition (X) is extremely effective for imparting high flexibility and transparency to the laminated sheet, but the component (A1) is a normal linear shape. Since it is a polypropylene, there are few high melt tension components, and it has the problem of thickness instability at the time of shaping | molding unexpectedly, such as thickness reduction at the time of heat sealing.

Therefore, if the molecular weight distribution of the component (A) is expanded to increase the relatively high molecular weight component, that is, the high melt tension component, the low molecular weight component inevitably increases, and as a result, it bleeds out to the sheet surface. This causes problems such as stickiness and poor appearance, and is not suitable for applications that require transparency. Further, in the expansion of the molecular weight distribution in a normal polypropylene having no branch, it is not sufficient to secure a high melt tension component. Therefore, it is desirable to secure a high melt tension component with a specific polypropylene resin having a branch.
By adding a specific amount of component (C) to component (A) with a low high melt tension component, the high melt tension component can be increased without increasing the low molecular weight component. As a result, the bleed out It is possible to suppress appearance defects such as thickness fluctuations and interface roughness and thinning during heat sealing without causing appearance defects such as.

  Component (C) is a polypropylene resin having a branch satisfying the following condition (C-i), preferably further satisfies the following (C-ii) to (C-iv), more preferably further: The following (Cv) to (C-vi) are satisfied.

(Ci) Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
(C-ii) In molecular weight distribution by GPC, Mw / Mn is 3.0 or more and 10.0 or less, and Mz / Mw is 2.5 or more and 10.0 or less. (C-iii) MFR is 0.1-30 g / 10 minutes (C-iv) 25 ° C. Paraxylene soluble component amount (CXS) is less than 5.0% by weight relative to the total amount of polypropylene resin (X) (Cv) Branching index g ′ when absolute molecular weight Mabs is 1 million Is 0.30 or more and less than 1.00 (C-vi) 95 mm or more of the mm chain fraction of propylene units by ¹³ C-NMR

(I): Melt tension (MT)
The component (C) used in the present invention has the following relationship between melt tension (MT) and MFR:
log (MT) ≧ −0.9 × log (MFR) +0.7
Or MT ≧ 15
You need to meet one of the following:
Here, MT is Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. Capillary: diameter 2.0 mm, length 40 mm, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, take-off speed: 4. The melt tension when measured under the conditions of 0 m / min and temperature: 230 ° C. is expressed in grams. However, when the MT of component (C) is extremely high, the resin may break at a take-up speed of 4.0 m / min. The tension at the speed of is defined as MT. The measurement conditions and units of MFR are as described above.

This rule is an index for the component (C) to have sufficient melt tension for moldability and suppression of thinning after heat sealing. Generally, MT has a correlation with MFR. It is described by a relational expression with MFR.
Thus, the method of defining the melt tension MT by the relational expression with MFR is a normal method for those skilled in the art. The following relational expression has been proposed.
log (MS)> − 0.61 × log (MFR) +0.82
(Here, MS is synonymous with MT.)
Japanese Unexamined Patent Application Publication No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR ^−0.7854 ≦ MT
Furthermore, Japanese Patent Laid-Open No. 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
MT ≧ 7.52 × MFR ^−0.576

In the present invention, the component (C) is a relational formula:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
If either of these is satisfied, it can be said that the resin has a sufficiently high melt tension, and is useful for suppressing moldability and thinning after heat sealing.
In addition, the component (C) has the following relational expression:
log (MT) ≧ −0.9 × log (MFR) +0.9 or MT ≧ 15
It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill the following relational expressions.
log (MT) ≧ −0.9 × log (MFR) +1.1 or MT ≧ 15
Although it is not necessary to provide the upper limit value of MT in particular, when MT exceeds 40 g, the take-up speed is remarkably slowed by the measurement method described above, and measurement becomes difficult. In such a case, since it is considered that the spreadability of the resin is also deteriorated, it is preferably 40 g or less, more preferably 35 g or less, and most preferably 30 g or less.

  In order to satisfy the relational expression of MT and MFR, the long chain branching amount of the component (C) may be increased to increase the melt tension. This can be achieved by controlling the amount ratio and prepolymerization conditions and introducing many long chain branches.

(Ii): Molecular weight distribution by GPC Further, the component (C) needs to have a relatively wide molecular weight distribution, and the molecular weight distribution Mw / Mn obtained by gel permeation chromatography (GPC) (where Mw is The weight average molecular weight (Mn is the number average molecular weight) is preferably 3.0 or more and 10.0 or less. The molecular weight distribution Mw / Mn of the component (C) is more preferably 3.5 to 8.0, and still more preferably 4.1 to 6.0.
Furthermore, it is preferable that Mz / Mw (where Mz is the Z average molecular weight) is 2.5 or more and 10.0 or less as a parameter that more significantly represents the width of the molecular weight distribution. A more preferable range of Mz / Mw is 2.8 to 8.0, and more preferably 3.0 to 6.0.
As the molecular weight distribution is wider, the moldability is improved, but when Mw / Mn and Mz / Mw are in this range, the moldability is particularly excellent.

The definitions of Mn, Mw, and Mz are described in “Basics of Polymer Chemistry” (Edited by Polymer Society, Tokyo Kagaku Dojin, 1978) and can be calculated from molecular weight distribution curves by GPC.
And the specific measuring method of GPC is as follows.
Apparatus: 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: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.

Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

  In order to set Mw / Mn to 3.0 or more and 10.0 or less and Mz / Mw to 2.5 or more and 10.0 or less, the temperature and pressure conditions of propylene polymerization are changed, or as the most general technique Can be easily adjusted by a method in which a chain transfer agent such as hydrogen is added during propylene polymerization. Furthermore, when using 2 or more types of the metallocene catalyst mentioned later and a catalyst, it can control by changing the quantity ratio.

(Iii): MFR
The melt flow rate (MFR) of the component (C) used in the present invention is preferably in the range of 0.1 to 30 g / 10 minutes, more preferably 0.3 to 20.0 g / 10 minutes, and still more preferably. 0.5 to 10.0 g / 10 min. Below this range, fluidity is insufficient and problems such as excessive load on the extruder during molding are likely to occur.On the other hand, those exceeding the range are not suitable for high melt tension materials due to insufficient tension. It tends to be something that is not.
The method for controlling the MFR value is well known, and can be easily adjusted by adjusting the temperature and pressure, which are the polymerization conditions of component (C), or by controlling the amount of hydrogen added to the chain transfer agent such as hydrogen during polymerization. Can be done.

(Iv): 25 ° C. para-xylene soluble component amount (CXS)
The component (C) used in the present invention has high stereoregularity, and it is preferable that there are few low crystallinity components that cause stickiness and bleed-out when it becomes a product. This low crystalline component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C., and it is preferably less than 5.0% by weight, more preferably 3.0% based on the total amount of component (C). % By weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. The lower limit is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.03% by weight or more.

The details of the CXS measurement method are as follows.
A 2 g sample is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to make a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is filtered off, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover room temperature xylene soluble components. The ratio (% by weight) of the weight of the recovered component to the charged sample weight is defined as CXS.

  In order to make CXS less than 5% by weight, it can be produced by using a metallocene catalyst, as will be described later. It is necessary that the reaction conditions are not extremely high and that the amount ratio of the organoaluminum compound to the metallocene complex is not increased too much.

(V): Branch index g ′
As a direct indicator that the component (C) used in the present invention has long chain branching, a branching index g ^′ can be mentioned. g ^′ is given by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. When a long chain branched structure is present, the value is smaller than 1.
The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index known to those skilled in the art.

The branching index g ^′ can be obtained as a function of the absolute molecular weight Mabs, for example, by using a GPC equipped with a light scatterometer and a viscometer as described below in the detector.
The component (C) used in the present invention preferably has a g 'of 0.30 or more and less than 1.00, more preferably 0.55 or more and 0 when the absolute molecular weight Mabs determined by light scattering is 1,000,000. .98 or less, more preferably 0.75 or more and 0.96 or less, and particularly preferably 0.78 or more and 0.95 or less.
The component (C)) used in the present invention is considered to preferably have a comb chain as a molecular structure. When the branching index g ′ is less than 0.30, the main chain is small and the side chain is The ratio is extremely large, and in such a case, the melt tension may not be improved or a gel may be formed, which is not preferable for sheet use. On the other hand, in the case of 1.00, this means that there is no long chain branching, the melt tension tends to be insufficient, and it is not suitable for moldability and suppression of thinning after heat sealing.
The lower limit of g ′ is preferably the above value for the following reason.
According to the document “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p.485), the g ^′ value of the comb polymer is represented by the following formula.

Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches. According to this equation, the number of branches is extremely large with a comb chain, that is, p is infinite, and g ^′ = g ^ε = λ ^ε , which is not less than the value of λ ^ε. In general, there will be a lower limit.

On the other hand, the formula of a conventionally known random branched chain that is considered to occur in the case of electron beam irradiation or peroxide modification is given by the formula (19) on page 485 in the same document. In the chain, as the number of branch points increases, the g ′ and g values monotonously decrease, especially without the lower limit. That is, in the present invention, the fact that the g ′ value has a lower limit means that the component (C) having a long chain branching structure used in the present invention has a structure close to a comb chain. Thereby, the distinction from the random branched chain produced | generated by the conventional electron beam irradiation or peroxide transformation becomes clearer.
Further, in the branched polymer having a structure close to a comb chain in which g ′ is in the above range, the degree of decrease in the melt tension when the kneading is repeated is small. When the end material generated by cutting the portion is subjected to molding again as a recycled material, the decrease in physical properties and moldability is reduced.

A specific method for calculating the branching index g ′ is as follows.
Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with an antioxidant Irganox 1076 manufactured by BASF Japan Ltd. at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.

In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

The branching index g ′ is a ratio of the intrinsic viscosity ([η] br) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity ([η] lin) obtained separately by measuring a linear polymer ([[ η] br / [η] lin).
When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of inertia becomes smaller, the intrinsic viscosity ([η] br) of the branched polymer with respect to the intrinsic viscosity ([η] lin) of the linear polymer having the same molecular weight as the long chain branched structure is introduced. ) Ratio ([η] br / [η] lin) becomes smaller.
Therefore, when the branch index (g ′ = [η] br / [η] lin) is a value smaller than 1, it means that a branch is introduced. Here, as a linear polymer for obtaining [η] lin, a commercially available homopolypropylene (Novatech PP (registered trademark), grade name: FY6 manufactured by Nippon Polypro Co., Ltd.) is used. The fact that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight is known as the Mark-Houwink-Sakurada equation, so [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Extrapolation can be used to obtain numerical values.

  In order to make the branching index g ′ 0.30 or more and less than 1.00, it is achieved by introducing many long-chain branches, selection of preferred metallocene catalysts described later, a combination thereof, a quantitative ratio thereof, and prepolymerization This can be achieved by controlling the conditions for polymerization.

(Vi): mm fraction of 3 chain of propylene units by ¹³ C-NMR The component (C) used in the present invention preferably has high stereoregularity. Stereoregularity of the ^height 13 that can be evaluated by ^{C-NMR, 13 C-NMR} mm fraction of the propylene unit triad sequences obtained by it is preferably 95% or more.
As for the mm fraction, the upper limit of the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same in any three propylene unit chains composed of head-to-tail bonds in the polymer chain is 100%. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control. If the mm fraction is smaller than this value, the mechanical properties tend to decrease.
Accordingly, the mm fraction is preferably 95% or more, more preferably 96% or more, and still more preferably 97% or more.

In addition, 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 is 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 sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. 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 analysis of the mm fraction is performed using the measured ¹³ C-NMR spectrum.
The spectrum is assigned with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30, vol. 1, 1350 (1989).
Note that a more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of Japanese Patent Laid-Open No. 2009-275207, and the present invention is performed according to this method. .

  The mm fraction can be 95% or more by using a polymerization catalyst that achieves a highly crystalline polymer, and by using a preferred metallocene catalyst described later for polymerization.

-Production method of polypropylene resin (C) having a branched structure Polypropylene resin (C) having a branched structure is not particularly limited as long as the above-described properties (i) to (vi) are satisfied. As described above, a preferable production method for satisfying all the conditions of low low crystalline component amount, high stereoregularity, relatively wide molecular weight distribution, range of branching index g ^′ , and high melt tension is a metallocene catalyst. This is a method using a macromer copolymerization method using a combination. As an example of such a method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 can be given.
This technique uses a catalyst having a specific structure having a macromer generation ability and a specific structure having a high molecular weight and a macromer copolymerization ability to produce a polypropylene having a long chain branched structure. According to this method, 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. Thus, it is possible to produce a polypropylene resin having a long chain branched structure having the desired physical properties.

In the past, it was necessary to increase the branching efficiency by lowering the crystallinity by using a polypropylene component having a low stereoregularity. However, in the above method, a polypropylene component having a sufficiently high stereoregularity is required. The above (vi) and (iv) relating to high stereoregularity and low amount of low crystalline component, which can be introduced into the side chain by a simple method and is preferable as the polypropylene resin (C) used in the present invention. It is suitable for satisfying these characteristics.
Moreover, if the said method is used, molecular weight distribution can be widened by using two types of catalysts from which a superposition | polymerization characteristic differs greatly, and the said (i)-required for the polypropylene resin (C) which has a branched structure used for this invention It is possible to satisfy the characteristics (ii) and (v) at the same time, which is preferable.

Therefore, a preferred method for producing a polypropylene resin (C) having a branched structure used in the present invention will be described in detail below.
A preferred method for producing a polypropylene resin (C) having a branched structure includes a method for producing a propylene-based polymer using the following catalyst components (M), (N) and (O) as propylene polymerization catalysts.
(M): at least one from component [M-1] which is a compound represented by the following general formula (m1) and at least from component [M-2] which is a compound represented by the following general formula (m2) One type, two or more types of transition metal compounds of Group 4 of the periodic table.
(N): Ion exchange layered silicate.
(O): Organoaluminum compound.

Hereinafter, the catalyst components (M), (N), and (O) will be described in detail.
・ Catalyst component (M)
(I) Component [M-1]: Compound represented by the following general formula (m1)

[In General Formula (m1), R ¹¹ and R ¹² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. R ¹³ and R ¹⁴ each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, having 6 to 16 carbon atoms An aryl group, a heterocyclic group containing 6 to 16 carbon atoms, nitrogen, oxygen or 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, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples 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 may contain a plurality of hetero elements selected from these, the aryl group In the range of 6 to 16 carbon atoms, one or more hydrocarbon group having 1 to 6 carbon atoms, silicon-containing hydrocarbon group having 1 to 6 carbon atoms, 1 to 6 carbon atoms on the aryl cyclic skeleton It may have a halogen-containing hydrocarbon group as a substituent.

At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, or 2,3-dimethyl. A phenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably a phenyl group, 4-i-propylphenyl group, 4- t-butylphenyl group, 4-trimethylsilylphenyl group, 4-chlorophenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (m1), X ¹¹ and Y ¹¹ are auxiliary ligands, and react with the co-catalyst of the catalyst component (N) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Indicates a group.
Further, in the general formula (m1), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms Either a good silylene group or a germylene group is shown. When two hydrocarbon groups are present on the silylene group or the 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 ( n-propyl) silylene, di (i-propyl) silylene, alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group And so on.
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 (m1), 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 dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( -Methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2 -Furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] Hough , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4 -(1-Naphtyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9- Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] ha Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2- Furyl) -4- (9-phenanthryl) -indenyl}] hafnium.

  Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

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

(Ii) Component [M-2]: Compound represented by the general formula (m2)

[In General Formula (m2), R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ each independently represent halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
In addition, R ²³ and R ²⁴ each independently contain a halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferable 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, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ²¹ and Y ²¹ are auxiliary ligands, and react with the co-catalyst of the catalyst component (N) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 silicon-containing hydrocarbon group, C1-C20 halogenated hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, amino group, or C1-C20 nitrogen-containing hydrocarbon group Indicates.

Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene 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 of Q ²¹ include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, Examples include diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene, and the like.

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

As non-limiting examples of the metallocene compound represented by the general formula (m2), the following can be preferably exemplified.
However, the following describes only representative exemplary compounds avoiding many complicated examples, and the present invention is not construed as being limited to these compounds, and various ligands, cross-linking groups or It is self-evident that auxiliary ligands can optionally be used. In the following, a compound in which the central metal is hafnium is described, but a compound replacing zirconium is also treated as disclosed in this specification.

  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- ( -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)- -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] 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}] huff Nitrogen, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] 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-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′- (9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Funium, 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-hydroazulenyl}] 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.

・ Catalyst component (N)
The catalyst component (N) preferably used for producing the polypropylene resin (C) is an ion-exchange layered silicate.
..Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces composed of ionic bonds, etc., stacked in parallel with each other with a binding force. This refers to a silicate compound having a crystal structure and containing exchangeable ions. Most silicates are mainly produced as a main component of clay minerals in nature, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. Good. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (N).
The silicate to be used is not limited to a natural product, and may be an artificial synthetic product or may contain 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 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.

.. Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of the catalyst component (N) can be used as it is without any particular treatment, but it is preferable to perform a chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate can 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 some or all of the cations of Al, Fe, Mg, etc. in the crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In addition, you may use what combined the following acids and salts as a processing agent. Moreover, the combination of these acids and salts may be sufficient.

-Salt treatment Preferably, 40% or more, more preferably 60% or more of the exchangeable Group 1 metal cations contained in the ion-exchange layered silicate before treatment with salts are dissociated from the salts shown below. It is preferable to exchange ions with the 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, 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

Preferred examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O ₄ , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.

Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

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

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

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

-Organic substance treatment Examples of the organic treating agent used for the organic substance treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (N).

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

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

  The ion-exchange layered silicate is preferable because it can be treated with a catalyst component (O) of an organoaluminum compound described later before use as a catalyst or as a catalyst. Although there is no restriction | limiting in the usage-amount of the catalyst component (O) 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 prepolymerization or slurry polymerization described later is used.

The catalyst component (N) is preferably a spherical particle having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

・ Catalyst component (O)
The catalyst component (O) is an organoaluminum compound. Organic aluminum compounds used as the catalyst component (O) is the general ^{_{formula: (AlR 31 q Z 3-}} q) a compound represented by _p is suitable.
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 ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, a hydrogen atom, 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 ³¹ is preferably an alkyl group, and Z is a chlorine atom when it is halogen, a C 1-8 alkoxy group when it is an alkoxy group, and a carbon atom number 1 when it is an amino group. An amino group of ˜8 is 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, it is trialkylaluminum in which R ³¹ is an alkyl group having 1 to 8 carbon atoms.

Catalyst formation / preliminary polymerization The catalyst is prepared by contacting each of the catalyst components (M) to (O) in the (preliminary) polymerization tank, simultaneously or continuously, or once or multiple times. Can be formed.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC-150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When the catalyst component (O) is used, before the catalyst component (M) and the catalyst component (N) are contacted, the catalyst component (M), or the catalyst component (N), or the catalyst component (M) and the catalyst Contacting the catalyst component (O) with both of the components (N), or contacting the catalyst component (O) simultaneously with contacting the catalyst component (M) and the catalyst component (N), or the catalyst component Although it is possible to contact the catalyst component (O) after bringing the catalyst component (N) into contact with the catalyst component (N), preferably, the catalyst component (M) is contacted with the catalyst component (N) before contacting the catalyst component (N). This is a method of contacting any of the component (O).
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 (M), (N) and (O) used is arbitrary. For example, the amount of the catalyst component (M) used relative to the catalyst component (N) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (N). The amount of the catalyst component (O) with respect to the catalyst component (M) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably within a range of 0.1 to 1 × 10 ^4. .

The component [M-1] (compound represented by the general formula (m1)) and the component [M-2] (compound represented by the general formula (m2)) are used in a proportion of the polypropylene resin (C). The molar ratio of the transition metal of [M-1] to the total amount of the components [M-1] and [M-2] is preferably within a range satisfying the above characteristics, but is preferably 0.30 or more, 0.0. 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 [M-1], a low molecular weight terminal vinyl macromer is produced, and from the component [M-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [M-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 branching index g ′, melt tension, and spreadability can be controlled.

In order to produce a polypropylene resin (C) having a branched structure, the molar ratio is preferably 0.30 or more, more preferably 0.40 or more, and further preferably 0.5 or more. Further, the upper limit is preferably 0.99 or less, and in order to efficiently obtain a polypropylene resin (C) with high catalytic activity, it is preferably 0.95 or less, more preferably 0.90 or less. It is a range.
Further, by using the component [M-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 is preferably subjected to a prepolymerization treatment which consists of contacting it with an olefin and polymerizing it in a small amount. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt physical properties can be improved thereby.

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

Use of catalyst / Propylene polymerization Any polymerization method can be used as long as the olefin polymerization catalyst including the catalyst component (M), catalyst component (N) and catalyst component (O) is in efficient contact with the monomer. Yes.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.

The polymerization temperature is usually 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
The polymerization pressure is preferably 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. 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 an activity improving effect, hydrogen is supplementarily in a molar ratio with respect to propylene, preferably in the range of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less. Can be used.

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 characterizing polypropylene having a long chain branching structure such as MFR, branching index, melt tension MT, and spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

In addition to the propylene monomer, copolymerization using an α-olefin comonomer having 2 to 20 carbon atoms excluding propylene, for example, ethylene and / or 1-butene as a comonomer may be performed depending on the application.
Therefore, in order to obtain a polypropylene resin (C) used in the present invention having a good balance between catalytic activity and melt properties, ethylene and / or 1-butene should be used at 15 mol% or less with respect to propylene. Is more preferable, it is 10 mol% or less, More preferably, it is 7 mol% or less.

  When propylene is polymerized using the catalyst and polymerization method exemplified here, one end of the polymer is mainly propenyl from an active species derived from the catalyst component [M-1] by a special chain transfer reaction generally called β-methyl elimination. The structure is shown and so-called macromers are produced. This macromer can generate a higher molecular weight and is taken into the active species derived from the catalyst component [M-2] having better copolymerizability, and the macromer copolymerization is considered to proceed. Therefore, it is considered that the comb chain is the main branch structure of the polypropylene resin having a long chain branch structure to be generated.

-Proportion of component (C) in propylene-based resin composition (X) The proportion of component (C) in propylene-based resin composition (X) is that of component (A), component (B), and component (C). It is necessary to be in the range of 1 to 50 wt% with respect to the total amount of 100 wt%. When content of a component (C) is less than 1 wt%, the provision of a moldability and the thinning suppression effect after heat seal is inadequate. On the other hand, when the content of the component (C) is too large, transparency and flexibility are deteriorated and a good sheet physical property balance cannot be obtained.

<Outer layer (2)>
In the sheet of the present invention, it is preferable to arrange an outer layer (2) in addition to the main layer (1) composed of the propylene-based resin composition (X). When providing an outer layer, it is not contrary to the meaning of this invention to provide arbitrary layers, for example, an adhesive layer, as needed between the main layer (1) and the outer layer (2).
In the case where the outer layer is provided, the main layer (1) is hereinafter referred to as the inner layer (1).
The outer layer (2) is not particularly limited as long as heat resistance and transparency are not impaired, and examples thereof include polyester resins, cyclic olefin resins, and propylene resins. Among these, it is preferable to form from a propylene-type resin composition (Y).

-Properties of propylene resin composition (Y) The propylene resin composition (Y) (hereinafter sometimes referred to as component (Y)) that is preferably used as the outer layer (2) of the propylene resin sheet is transparent. It is important that the heat resistance is excellent. In order to obtain transparency as a sheet, not only the inner layer (1) but also the outer layer (2) must be made transparent. In addition, the outer layer (2) must also have heat resistance, must not be deformed even by heat treatment such as sterilization and sterilization, and must not stick to the heat seal bar in the secondary heat seal. is there.

  In order to satisfy these requirements at a high level, the propylene-based resin composition (Y) includes a propylene-based resin (D) having a melting peak temperature Tm (D) in the range of 150 to 170 ° C. (hereinafter, component (D)). It may be said that it contains.) It is preferable to contain.

(Di) Melting peak temperature Tm (D)
The melting peak temperature Tm (D) of the component (D) is preferably in the range of 150 to 170 ° C, more preferably 155 to 170 ° C, still more preferably 158 to 168 ° C.
When Tm (D) is less than 150 ° C., the heat resistance is insufficient, and there is a problem that the heat seal bar tends to stick to the heat seal. Those having a Tm (D) exceeding 170 ° C. are difficult to produce industrially.

(D-ii) Melt flow rate MFR (D)
Component (D) has an appropriate fluidity in order to obtain easy moldability that does not cause interface roughness and surface roughness during lamination and does not cause thickness fluctuations. The scale, melt flow rate MFR (230 ° C., 2.16 kg load) (hereinafter sometimes referred to as MFR (D)) is preferably in the range of 2 to 20 g / 10 minutes, and 2 to 15 g / 10. More preferably, it is in the range of minutes, and more preferably 4 to 15 g / 10 minutes.
When the MFR (D) is less than 2 g / 10 minutes, roughening of the interface and roughening of the surface are likely to occur, and a sheet having a good appearance may not be obtained. On the other hand, when MFR (D) exceeds 20 g / 10 minutes, thickness fluctuation is likely to occur, and moldability is often difficult.
Here, MFR is a value measured according to JIS K7210.

-Production method of component (D) The propylene-based resin (D) used in the present invention may be a propylene homopolymer as long as the above melting point range is satisfied, a random copolymer with another α-olefin, or It may be a block copolymer with another α-olefin.
Such component (D) may be produced by any method. When producing a composition comprising a propylene-based (co) polymer component (D1) and a propylene-ethylene random copolymer (D2) (so-called block polymer), the propylene-based (co) heavy produced separately Propylene-based (co) polymer (D1) is produced even if the blend (D1) and propylene-ethylene random copolymer (D2) are produced by using a mixing device to produce a propylene-based resin (D). The propylene-ethylene random copolymer (D2) may be produced in the presence of the system (co) polymer (D1) to continuously produce the propylene resin (D).

  In addition, a component (D) can also be suitably selected from what is marketed, and can also be used. Examples of commercially available products include Nippon Polypro's product name Novatec PP, Nippon Polypro's product name Newcon (NEWCON), Mitsubishi Chemical's product name Zelas (ZELAS), and the like. In these uses, a grade satisfying the melting peak temperature and MFR which are the conditions of the present invention may be appropriately selected.

・ Modifier (D3)
The following elastomer component (D3) may be added to the propylene-based resin (D) in order to impart impact resistance at a lower temperature.
As an elastomer component which can be mix | blended with the outer layer (2) of a propylene-type resin sheet, an ethylene-alpha-olefin copolymer and a styrene-type elastomer are mentioned, for example. The ethylene-α-olefin copolymer is a copolymer obtained by copolymerizing ethylene and preferably an α-olefin having 3 to 20 carbon atoms, and the α-olefin is a copolymer having 3 to 20 carbon atoms. Preferred examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-heptene.
As an ethylene-α-olefin copolymer that can be suitably used in the present invention, it is necessary to match the density in order to reduce the difference in refractive index from the component (D). In order to suppress, it is desirable that crystallinity and molecular weight distribution are narrow. Therefore, it is desirable to use a polymerized with a metallocene catalyst that can narrow the crystallinity and molecular weight distribution.

In addition, the ethylene-alpha-olefin copolymer as a component (D3) can also be suitably selected from what is marketed as a metallocene polyethylene, and can also be used.
Examples of commercially available products include DuPont Dow's trade name affinity (AFFINITY) and Engage (ENGAGE), Nippon Polyethylene's trade name kernel (KERNEL), ExxonMobil's trade name Exact (EXACT), and the like. In these uses, the density and MFR may be appropriately selected so as to cause problems such as transparency, stickiness, and bleed out.
Moreover, as a styrene-type elastomer, it can select and use suitably from what is marketed. For example, as a hydrogenated styrene-butadiene block copolymer, “Clayton G” from Clayton Polymer Japan Co., Ltd., and “Tuftec” from Asahi Kasei Kogyo Co., Ltd. Kuraray Co., Ltd. under the trade name “Septon”, and styrene-vinylated polyisoprene block copolymer as a hydrogenation product under the product name “Hibler”, under the trade name “Styrene”. A hydrogenated product of the copolymer is sold under the trade name “Dynalon” by JSR Corporation, and may be appropriately selected from these product groups.

-Ratio of each component in component (Y) in outer layer When using component (D3) which can be used suitably for this invention, the ratio for which component (D) occupies in the outer layer (2) structure is 60 to 99 wt% The proportion of the component (D3) in the outer layer (2) structure is preferably in the range of 1 to 40 wt%. More preferably, the content of the component (D) is 70 to 95 wt%, and the content of the component (D3) is 5 to 30 wt%.
When the content of the component (D) is less than 60 wt%, that is, when the content of the component (D3) is 40 wt% or more, the heat resistance is insufficient and there is a possibility that deformation occurs in the heat treatment process. When the content of the component (D) is 99 wt% or more, that is, when the content of the component (D3) is less than 1 wt%, the low temperature impact resistance imparting effect is insufficient.

<Innermost layer (3)>
The sheet of the present invention is also preferably a sheet comprising at least three layers having the innermost layer (3) in the order of the outer layer (2), the inner layer (1), and the innermost layer (3). The innermost layer (3) is provided for controlling the heat sealability of the sheet, or for imparting a low temperature sealability or easy peelability, but the purpose thereof is not limited.
The resin composition (Z) used for the innermost layer is not particularly limited, and various types of resins can be used depending on the purpose. It is preferable to have appropriate fluidity in order to obtain easy moldability that does not cause thickness fluctuations, and the melt flow rate MFR (230 ° C., 2.16 kg load) is in the range of 2 to 15 g / 10 min. Preferably, it is 2.5 to 10 g / 10 min.
When the MFR (also referred to as MFR (Z)) of the resin composition (Z) is less than 2 g / 10 minutes, roughening of the interface and roughening of the surface are likely to occur, and a sheet having a good appearance may not be obtained. On the other hand, when MFR (Z) exceeds 15 g / 10 min, thickness variation is likely to occur, and moldability is difficult.
Here, MFR is a value measured according to JIS K7210.

Propylene-based resin composition or propylene comprising a propylene-ethylene random copolymer produced using a metallocene catalyst and an ethylene-α olefin copolymer produced using a metallocene catalyst as preferred components used in the innermost layer A propylene-based resin composition comprising the resin-based resin composition (A), the modifier (B), and the propylene-based resin (D) can be preferably exemplified.
As a commercial item of the propylene-ethylene random copolymer manufactured using the metallocene catalyst, the trade name “WINTEC” manufactured by Nippon Polypro Co., Ltd. can be exemplified, and the ethylene-α-olefin copolymer Examples of commercially available products include DuPont Dow's trade name affinity (AFFINITY) and Engage (ENGAGE), Nippon Polyethylene's trade name kernel (KERNEL), ExxonMobil's trade name Exact (EXACT), and the like.

<Additional ingredients (additives)>
The propylene resin compositions (X), (Y), and (Z) used for the inner layer (1), outer layer (2), and innermost layer (3) in the propylene resin sheet of the present invention are preferably used as a sheet. Therefore, any additive or resin can be blended within a range that does not significantly impair the effects of the present invention, such as bleeding out.
Examples of such optional components include antioxidants, crystal nucleating agents, clearing agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, neutralizing agents, and metal inertness used in ordinary polyolefin resin materials. Examples thereof include a colorant, a colorant, a dispersant, a peroxide, a filler, a fluorescent brightening agent, and a polyethylene resin. Furthermore, an elastomer can be mix | blended as a component which provides a softness | flexibility in the range which does not impair the effect of this invention remarkably.
Various additives and resins are described in detail below.

(I) Antioxidants As antioxidants, specific examples of phenolic antioxidants include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10- Examples thereof include tetraoxaspiro [5,5] undecane, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like.

Specific examples of phosphorus antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, bis (2, 4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t -Butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phos You can list s fights.
Specific examples of the sulfur-based antioxidant include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, pentaerythritol-tetrakis- (3-lauryl-thio-propionate), and the like. it can.
These antioxidants can be used singly or in combination of two or more, as long as the effects of the present object are not impaired.

  The blending amount of the antioxidant is 0.01 to 1.0 part by weight, preferably 0.02 to 0.5 part by weight, and more preferably 0.05 to 0.1 part by weight with respect to 100 parts by weight of each resin. When the parts by weight and the blending amount are less than the above ranges, the effect of thermal stability cannot be obtained, and deterioration occurs during the production of the resin, causing burns and causing fish eyes. On the other hand, when the above range is exceeded, it becomes a foreign substance and causes fish eyes, which is not preferable.

(Ii) Anti-blocking agent The anti-blocking agent has an average particle diameter of 1 to 7 μm, preferably 1 to 5 μm, more preferably 1 to 4 μm. If the average particle diameter is less than 1 μm, the slipperiness and openability of the resulting sheet are inferior, which is not preferable. On the other hand, if it exceeds 7 μm, transparency and scratch resistance are remarkably inferior. Here, the average particle diameter is a value obtained by Coulter counter measurement.

Specific examples of the anti-blocking agent include, for example, inorganic or synthetic silica (silicon dioxide), magnesium silicate, aluminosilicate, talc, zeolite, aluminum borate, calcium carbonate, calcium sulfate, barium sulfate, calcium phosphate. Etc. are used.
Moreover, as an organic type, polymethyl methacrylate, polymethylsilyltosesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde (urea resin), phenol resin, etc. may be used. it can.
In particular, synthetic silica and polymethyl methacrylate are preferable from the balance of dispersibility, transparency, blocking resistance, and scratch resistance.
Anti-blocking agents may be surface-treated, and as surface treating agents, surfactants, metal soaps, acrylic acids, oxalic acid, citric acid, tartaric acid and other organic acids, higher alcohols, esters , Silicone, fluorine resin, silane coupling agent, hexametaphosphate soda, pyrophosphoric acid soda, tripolyphosphate soda, trimetaphosphate soda, etc. can be used, especially citric acid treatment among organic acid treatment Those are preferred. The treatment method is not particularly limited, and a known method such as surface spraying or dipping can be employed.
The anti-blocking agent may have any shape, and may be any shape such as a spherical shape, a square shape, a column shape, a needle shape, a plate shape, or an indefinite shape.
These anti-blocking agents can be used singly or in combination of two or more in a range that does not impair the effects of this object.

  When the antiblocking agent is blended, the blending amount is 0.01 to 1.0 part by weight, preferably 0.05 to 0.7 part by weight, and more preferably 0.1 to 0 part by weight based on 100 parts by weight of the resin. .5 parts by weight. When the blending amount is less than the above range, the anti-blocking property, slipping property, and opening property of the sheet are likely to be inferior. When the above range is exceeded, the transparency of the sheet is impaired, and the sheet itself becomes a foreign substance, which causes fish eyes and is not preferable.

(Iii) Slip agent Examples of the slip agent include monoamides, substituted amides, bisamides, and the like, which can be used alone or in combination of two or more.
Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like as saturated fatty acid monoamides.
Examples of the unsaturated fatty acid monoamide include oleic acid amide, erucic acid amide, ricinoleic acid amide and the like.
Specific examples of substituted amides include N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide Etc.
Specific examples of bisamides include, as saturated fatty acid bisamides, methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, Ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bishydroxy stearic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl Sepacic acid amide and the like can be mentioned.
Examples of the unsaturated fatty acid bisamide include ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide and the like.
Examples of the aromatic bisamide include m-xylylene bis stearic acid amide and N, N′-distearylisophthalic acid amide.
Among these, oleic acid amide, erucic acid amide, and behenic acid amide are particularly preferably used among the fatty acid amides.

  As a compounding quantity in the case of mix | blending a slip agent, it is 0.01-1.0 weight part with respect to 100 weight part of resin, Preferably it is 0.05-0.7 weight part, More preferably, it is 0.1-0. .4 parts by weight. If it is less than the said range, opening property and slipperiness will become inferior easily. If the above range is exceeded, the slip agent will be excessively raised, bleeding on the sheet surface and the transparency will deteriorate.

(Iv) Nucleating agent Specific examples of the nucleating agent include 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4-di (p-methyl). A sorbitol compound such as benzylidene) sorbitol, hydroxy-di (t-butylaluminum benzoate), 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid and an aliphatic mono-carbon having 8 to 20 carbon atoms. Examples thereof include a carboxylic acid lithium salt mixture (manufactured by ADEKA, trade name NA21).
As a compounding quantity in the case of mix | blending the said nucleating agent, 0.0005-0.5 weight part with respect to 100 weight part of each resin, Preferably it is 0.001-0.1 weight part, More preferably, it is 0.00. 005 to 0.05 parts by weight. If it is less than the said range, the effect as a nucleating agent is not acquired. Exceeding the above range is undesirable because it itself becomes a foreign substance and causes fish eyes.

Moreover, a high density polyethylene resin can be mentioned as a nucleating agent other than the above. The density of the high-density polyethylene resin is 0.94 to 0.98 g / cm ³ , preferably 0.95 to 0.97 g / cm ³ . When the density is out of this range, the effect of improving transparency cannot be obtained. The melt flow rate (MFR) at 190 ° C. of the high-density polyethylene resin is 5 g / 10 min or more, preferably 7 to 500 g / 10 min, and more preferably 10 to 100 g / 10 min. When the MFR is less than 5 g / 10 min, the dispersion diameter of the high-density polyethylene resin is not sufficiently reduced, and the MFR itself becomes a foreign substance, which causes fish eyes. In order to finely disperse the high-density polyethylene resin, the MFR of the high-density polyethylene resin is preferably larger than the MFR of the propylene-based resin of the present invention.

  The production of the high-density polyethylene resin used as the nucleating agent is not particularly limited with respect to the polymerization method and catalyst as long as a polymer having the desired physical properties can be produced. For catalysts, Ziegler type catalysts (ie, based on a combination of supported or unsupported halogen-containing titanium compounds and organoaluminum compounds), Kaminsky type catalysts (ie, supported or unsupported metallocene compounds and organoaluminum compounds, especially alumoxanes). Based on the combination). There is no restriction | limiting about the shape of a high density polyethylene-type resin, A pellet form may be sufficient and a powder form may be sufficient.

  When used as a nucleating agent, the blending amount of the high-density polyethylene is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part with respect to 100 parts by weight of the resin. Parts by weight. If it is less than the said range, the effect as a nucleating agent will not be acquired. Exceeding the above range is undesirable because it itself becomes a foreign substance and causes fish eyes.

(V) Neutralizing agent Specific examples of the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite, Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.), and the like.
The blending amount when the neutralizing agent is blended is 0.01 to 1.0 part by weight, preferably 0.02 to 0.5 part by weight, and more preferably 0.05 to 0 part per 100 parts by weight of the resin. .1 part by weight. If the blending amount is less than the above range, the effect as a neutralizing agent cannot be obtained, and the deteriorated resin inside the extruder is scraped off, causing fish eyes. On the other hand, when the above range is exceeded, it becomes a foreign substance and causes fish eyes, which is not preferable.

(Vi) Light Stabilizer As the light stabilizer, a hindered amine stabilizer is preferably used, and a structure in which all hydrogens bonded to the 2nd and 6th carbons of a conventionally known piperidine are substituted with methyl groups. Although the compound which has this is used without being specifically limited, the following compounds are specifically used.
Specific examples include polycondensates of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6). -Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N-bis (3-aminopropyl) ) Ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4- Jil} {(2,2, , 6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], poly [(6-morpholino-s-triazine-2,4-diyl) And [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}].
These hindered amine stabilizers can be used singly or in combination of two or more in a range not impairing the effect of the present object.

When the hindered amine stabilizer is blended, the blending amount is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the resin. Is desirable.
If the content of the hindered amine stabilizer is less than 0.005 parts by weight, there will be no effect of improving the stability such as heat resistance and aging resistance, and if it is more than 2 parts by weight, the fish itself becomes a foreign substance. It causes an eye and is not preferable.

(Vii) Antistatic agent As the antistatic agent, any known antistatic agent or antistatic agent that has been conventionally used as an antistatic agent or an antistatic agent can be used without any particular limitation. For example, an anionic surfactant, Examples include cationic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactant include fatty acid or rosin acid soap, N-acyl carboxylate, ether carboxylate, carboxylate such as fatty acid amine salt; sulfosuccinate, ester sulfonate, N-acyl sulfonate Sulfonates such as salts; sulfated oils, sulfate esters, alkyl sulfate salts, sulfate sulfate polyoxyethylene salts, sulfate ether salts, sulfate ester salts such as sulfate amide salts; alkyl phosphate salts, alkyl polyoxyethylene phosphates Examples thereof include phosphoric acid ester salts such as salts, phosphoric acid ether salts and phosphoric acid amide salts.

  Examples of the cationic surfactant include amine salts such as alkylamine salts; alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethylammonium chloride, tetraalkylammonium salt, N, N-di Quaternary ammonium salts such as (polyoxyethylene) dialkylammonium salts and N-alkylalkanamide ammonium salts; 1-hydroxyethyl-2-alkyl-2-imidazoline, 1-hydroxyethyl-1-alkyl-2-alkyl Examples include alkyl imidazoline derivatives such as -2-imidazoline; imidazolinium salts, pyridinium salts, isoquinolinium salts, and the like.

  Examples of the nonionic surfactant include ether forms such as alkyl polyoxyethylene ether and p-alkylphenyl polyoxyethylene ether; fatty acid sorbitan polyoxyethylene ether, fatty acid sorbitol polyoxyethylene ether, fatty acid glycerin polyoxyethylene ether, etc. Ether ester form of fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sucrose ester, dihydric alcohol ester, boric acid ester, etc .; dialcohol alkylamine, dialcohol alkylamine ester, fatty acid alkanolamide, N, N-di (polyoxyethylene) alkanamide, alkanolamine ester, N, N-di (polyoxyethylene) alkaneamine, amine oxy De, a nitrogen-formed and fabricated and alkyl polyethylene imine.

  Examples of the amphoteric surfactant include amino acid forms such as monoaminocarboxylic acid and polyaminocarboxylic acid; N-alkyl-β-alanine such as N-alkylaminopropionate and N, N-di (carboxyethyl) alkylamine salt. Forms: Betaine forms such as N-alkylbetaines, N-alkylamidobetaines, N-alkylsulfobetaines, N, N-di (polyoxyethylene) alkylbetaines, imidazolinium betaines; 1-carboxymethyl-1-hydroxy- And alkyl imidazoline derivatives such as 1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

  Among these, nonionic surfactants and amphoteric surfactants are preferable. Among them, monoglycerides, diglycerides, boric acid esters, dialcohol alkylamines, dialcohol alkylamine esters, amides and the like or nitrogen-containing non-type surfactants are preferred. Ionic surfactants; betaine amphoteric surfactants are preferred.

  In addition, as an antistatic agent, a commercial item can be used, for example, electro stripper TS5 (trade name, glycerin monostearate manufactured by Kao Corporation), electro stripper TS6 (trade name, stearyl manufactured by Kao Corporation). Diethanolamine), electrostripper EA (trade name, lauryl diethanolamine, manufactured by Kao Corporation), electrostripper EA-7 (trade name, polyoxyethylene laurylamine capryl ester, manufactured by Kao Corporation), Denon 331P (maruhishi oil ( Co., Ltd., trademark, stearyl diethanolamine monostearate), Denon 310 (manufactured by Maruhishi Oil Chemical Co., Ltd., trademark, alkyldiethanolamine fatty acid monoester), Register PE-139 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trademark) , Stearic acid mono & diglyceride Ester), Chemistat 4700 (Sanyo Chemical Industries Co., Ltd., trademark, alkyl dimethyl betaine), rheostat S (Lion Co., Ltd., trademark, alkyl diethanolamide), and the like.

  When blending the antistatic agent, the blending amount is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.8 parts by weight, based on 100 parts by weight of the resin. Most preferably, it is 0.2 to 0.5 parts by weight. These antistatic agents can be used singly or in combination of two or more in a range that does not impair the effects of this object. When the blending amount of the antistatic agent is less than 0.01 parts by weight, it is not possible to reduce the surface specific resistance and prevent the failure due to charging. On the other hand, when the amount is more than 2 parts by weight, powder blowing tends to occur on the sheet surface due to bleeding.

(Viii) Polyethylene resin As the polyethylene resin, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and the like can be arbitrarily added as long as the effects of the present invention are not significantly impaired.

<Manufacture of the resin composition which comprises each layer of a propylene-type resin sheet>
The propylene-based resin composition (X) constituting the inner layer (1) in the propylene-based resin sheet of the present invention includes the above-described propylene-based resin composition (A), the modifier (B), and a branched polypropylene resin (C In addition, other additional components are obtained by mixing with a Henschel mixer, V blender, ribbon blender, tumbler blender, etc., and if necessary, such as single screw extruder, multi-screw extruder, kneader, Banbury mixer, etc. It is obtained by a method of kneading with a kneader.

  The propylene-based resin composition (Y) constituting the outer layer (2) in the propylene-based resin sheet of the present invention comprises the above-described propylene-based resin (D) and other additional components as necessary, a Henschel mixer, a V blender. It is obtained by mixing with a ribbon blender, tumbler blender or the like and, if necessary, obtained by a kneading method using a kneader such as a single screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer.

The propylene-based resin composition (Z) constituting the innermost layer (3) in the propylene-based resin sheet of the present invention includes a desired resin component, other optional components as necessary, a Henschel mixer, a V blender, and a ribbon. It is obtained by mixing with a blender, tumbler blender or the like, and if necessary, it is obtained by a method of kneading with a kneader such as a single screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.
The above components may be mixed at the same time, or may be mixed and kneaded after making a part of the master batch.

<Propylene resin sheet>
The propylene-based resin sheet of the present invention can be produced by a known method using the propylene-based resin composition. For example, it is produced by a known technique such as extrusion using a T die or a circular die.

The propylene-based resin sheet of the present invention preferably has a thickness of 0.01 mm to 1.0 mm.
Moreover, the ratio of the inner layer when the thickness of the entire sheet is 100 is preferably 50 to 98, more preferably 60 to 90. If the ratio of the inner layer is less than 50, the flexibility and impact resistance tend to be poor, whereas if it exceeds 98, the heat resistance tends to be poor.
The outer layer of the propylene-based resin sheet of the present invention is preferably 2 or more and less than 50, more preferably 5 or more and less than 30 when the thickness of the entire sheet is 100.
When the innermost layer is further provided on the propylene-based resin sheet of the present invention, when the total thickness of the sheet is 100, it is preferably 2 or more and less than 48, more preferably 5 or more and less than 30.
The propylene-based resin sheet of the present invention is excellent in flexibility, transparency, impact resistance, heat resistance, cleanliness, can suppress deterioration of transparency due to poor appearance such as uneven thickness, rough interface, etc. Because of its excellent impact resistance, it is suitable for heat treatment packaging bags that require heat treatment steps such as sterilization and sterilization, particularly infusion bags.

The propylene-based resin sheet of the present invention is characterized by having excellent flexibility even after heat treatment, and it is desirable that the tensile elastic modulus, which is a measure of flexibility, is 400 MPa or less. When the tensile elastic modulus is 400 MPa or less, preferably 380 MPa or less, and more preferably 360 MPa, it is very excellent in that it has a good tactile sensation and can provide a high-class feeling.
The propylene-based resin sheet of the present invention has an internal haze (Haze), which is a measure of transparency, preferably 10% or less, more preferably 8% or less, and even more preferably 7% or less after heat treatment. It is very excellent in that the contents can be clearly seen and it can be confirmed whether or not there are foreign objects in the contents.

  The propylene-based resin sheet of the present invention is excellent in impact resistance, in particular, impact resistance at an extremely low temperature such as −20 ° C., and 5 kJ / in an impact strength test at −20 ° C., which is a measure of low temperature impact. It has excellent impact resistance of m or more, and is excellent in that it can be used as a product without being broken even if it is dropped in the transportation process or storage process.

In addition, the propylene-based resin sheet of the present invention has excellent heat resistance, and has excellent heat resistance that does not cause deformation even when heat treatment at around 121 ° C. is performed. The deformed one has a poor appearance and the product value is lowered, and cannot be used as a product.
In addition, the propylene-based resin sheet of the present invention has excellent cleanliness, and there are extremely low molecular weight components and low regularity components that may contaminate the contents in the innermost layer (3) in contact with the contents. It is desirable to use a propylene-based resin composition obtained using a small amount of metallocene catalyst.

Moreover, the propylene-type resin sheet of this invention has the high shape retention of the heat seal part at the time of heat sealing, and is excellent in secondary processability. Generally, when a propylene-based resin sheet is heat-sealed, the shape changes, that is, the heat-sealed part becomes thin, or a thick part is formed around the heat-sealed part. The shape retention here refers to the sheet thickness retention at the shape change as described above by heat sealing at 145 ° C., specifically, the heat sealing with respect to the thickness of the part that is not heat sealed. It is the ratio of the thickness of the part.
Details are determined by the following method.
That is, the propylene-based resin sheet is heat-sealed (heat-sealing conditions: pressure 3.4 kgf / cm ² , time 1.5 seconds, temperature 145 ° C.), and the heat-sealed portion is observed with an optical microscope. Measure the thickness of the unsealed part. The shape retention rate is expressed by the following formula.
Shape retention rate (%) = heat seal portion thickness ÷ thickness of non-heat sealed portion × 100
A sheet having a high shape retention rate has a sheet thickness, so that the sheet strength is also maintained, and the package is a good heat-sealed shape that is difficult to break. When the shape retention is 72% or more, thinning of the heat seal portion is suppressed and the strength is excellent, 75% or more is preferable, and 77% or more is particularly preferable.

  In the following, in order to describe the present invention more specifically and clearly, the present invention will be described in contrast to examples and comparative examples, demonstrating the rationality and significance of the requirements of the composition of the present invention. The present invention is not limited to these examples. The physical property measurement methods, characteristic evaluation methods, and resin materials used in Examples and Comparative Examples are as follows.

1. Method for measuring resin physical properties (a) MFR:
Propylene-based resin composition (A), branched polypropylene resin (C), and propylene-based resin (D) are in accordance with JIS K7210 A method condition M, test temperature: 230 ° C., nominal load: 2.16 kg, die shape: The measurement was performed at a diameter of 2.095 mm and a length of 8.00 mm.
In addition, an ethylene-α-olefin copolymer, which is a kind of modifier (B), is in accordance with JIS K7210 A method condition D, test temperature: 190 ° C., nominal load: 2.16 kg, die shape: diameter 2.095 mm. The length was measured at 8.00 mm.
(B) Density:
The density gradient tube method was used in accordance with JIS K7112 D method.
(C) Melting peak temperature:
Using a TA Instruments DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of 10 ° C./min, and further increase the rate at 10 ° C./min. The melting peak temperature when melted with was measured.

(D) Tan δ peak temperature measurement A sample cut into a strip shape of 10 mm width × 18 mm length from a 200 μm thick sheet obtained by water-cooled inflation molding under the following conditions was used. In addition, when it was difficult to detect stress when using a sheet having a thickness of 200 μm, the measurement was performed with two sheets stacked. As the apparatus, ARES manufactured by Rheometric Scientific was used. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
Water-cooled inflation molding (for propylene-based resin PP (A-1) described later):
As an extruder for inner layer, a single screw extruder with a diameter of 30 mm, a single screw extruder with a diameter of 18 mm as an extruder for outer layer and innermost layer, propylene resin A was introduced into all the extruders, and a mandrel diameter of 50 mm Extruded from a circular die with a Lip width of 1.0 mm at a set temperature of 200 ° C. and water-cooled with a water-cooled ring adjusted to 10 ° C., and water-cooled inflation molding was performed at a speed of 3 m / min so that the folding width was 90 mm. And a sheet having a thickness of 200 μm was obtained.

(E) Die Swell Measurement The die swell of the propylene-based resin composition (X) was measured under the following conditions using a capillograph manufactured by Toyo Seiki Seisakusho.
・ Capillary: diameter 3.8mm, length 8mm
・ Cylinder diameter: 9.55mm
・ Cylinder extrusion speed: 10 mm / min ・ Pickup speed: 10 m / min ・ Temperature: 190 ° C.
Die swell detector: Laser scan micrometer (LSM5100, manufactured by Mitutoyo Corporation)
-Die swell detection location: 10mm below the nozzle
・ Die swell measurement frequency: measured every 10 seconds (measured every 1.6 m)
-Number of die swell measurement points: 20 points (all 33m measurement)
The difference between the maximum value and the minimum value of the die swell is calculated. The larger the difference, the greater the variation in strand diameter, and the greater the variation in thickness in sheet molding. The smaller the difference, the smaller the variation in strand diameter. Variation in thickness is small. That is, the smaller the difference between the maximum value and the minimum value of the die swell, the better the sheet formability. If the difference is 0.25 or less, sufficient moldability is exhibited, and it is preferably 0.23 or less. 0.22 or less is particularly preferable.

(F) Amount of soluble component at 25 ° C. paraxylene (CXS, unit: wt%):
Measurement was performed according to the method described above.
(G) mm fraction:
Using a superconducting nuclear magnetic resonance apparatus GSX-400 (400 MHz) manufactured by JEOL Ltd. and FT-NMR, as described above, measurement was performed by the method described in paragraphs [0053] to [0065] of JP-A-2009-275207. .

(H) Molecular weight distributions Mw / Mn and Mz / Mn:
It was determined by GPC measurement according to the method described above.
(L) Branch degree g ':
As described above, it was determined by GPC equipped with a differential refractometer (RI), a viscosity detector (Viscometer), and a light scattering detector (MALLS) as detectors.

(Nu) Melt tension MT (unit: grams):
It measured on the following conditions using the Toyo Seiki Seisakusho Capillograph.
・ Capillary: Diameter 2.0mm, length 40mm
・ Cylinder diameter: 9.55mm
・ Cylinder extrusion speed: 20 mm / min ・ Pickup speed: 4.0 m / min ・ Temperature: 230 ° C.
When the MT is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and the tension at the highest speed at which the take-up can be taken is MT. And

(L) Amounts of components (A1) and (A2) W (A1) and W (A2) and α-olefin contents α [A1] and α [A2] of components (A1) and (A2) Measured by the method.

2. Sheet evaluation method (a) Heat resistance:
<Heat resistance evaluation of laminated sheets of Examples 1 to 3 and Comparative Example 1>
A cylindrical propylene-based resin sheet was cut into a size of 210 mm in the flow direction, and one of the cut out pieces was heat sealed using an impulse sealer to form a bag. Next, 250 ml of water was filled therein, and the other side was heat sealed using an impulse sealer and sealed. Sealing was performed such that the distance between the heat seal and the heat seal was 200 mm.
The sample bag thus obtained was put into a high-temperature and high-pressure cooking sterilization tester (manufactured by Nisaka Manufacturing Co., Ltd., RCS-40RTGN type) and then pressurized, and the ambient temperature was increased to 121 ° C. For 30 minutes. Then, it cooled to about 40 degreeC and took out this sample bag from the testing machine. (Hereinafter, the sterilized sheet (sample bag) may be referred to as a heat-treated sheet.)
The heat resistance evaluation of the heat-treated sheet was performed according to the following criteria.
×: Deformation, wrinkle, inner surface fusion occurred, unusable ○: Deformation, wrinkle, inner surface fusion occurred, or very slight and usable level In addition, in the item column of Table 6 of the evaluation results Was marked as appearance.

(B) Transparency (internal haze):
After the heat treatment, both surfaces of the laminated sheet were brought into close contact with a slide glass with liquid paraffin, and measured with a haze meter in accordance with JIS K7136-2000. The smaller the value obtained, the better the transparency. When this value is 10% or less, it is easy to confirm the contents and the display effect is excellent, and 8% or less is preferable. % Or less is particularly preferable.

(C) Flexibility (tensile modulus):
Based on JIS K7127-1989, the tensile elasticity modulus about the flow direction (MD) of the laminated sheet after heat processing was measured on condition of the following. The smaller the obtained value, the better the flexibility. When this value is 400 MPa or less, it is excellent in terms of obtaining a high-quality feeling with a good touch, preferably 380 MPa or less, and 360 MPa or less. Is particularly preferred.
Sample length: 110mm
Sample width: 10mm
Distance between chucks: 50mm
Crosshead speed: 0.5mm / min

(D) Impact strength (unit: KJ / m):
Using a Toyo Seiki film impact tester, the amount of work required for penetration failure per unit sheet thickness was measured. Specifically, after the heat treatment, the laminated sheet is left in an atmosphere at −20 ° C. for 24 hours or more, and after adjusting the state, the test sheet is fixed to a holder having a diameter of 50 mm at −20 ° C., and 12.7 mmφ The hemispherical metal penetrating portion was hit, and the brittleness to the impact of the sheet was measured from the work amount (KJ) required for the penetrating fracture. When this value is 5 KJ / m or more, it is excellent in that the bag breakage can be suppressed even after the transport process at a cryogenic temperature.

(E) Secondary processing suitability (shape retention rate):
A cylindrical propylene-based resin sheet is cut into a size of 100 mm in the flow direction, and one of the cut-outs is heat sealed (heat sealing condition: pressure 3.4 kgf / cm ² , time 1.5 seconds, temperature 145 ° C.) The condition was adjusted for 24 hours in an atmosphere of 23 ° C. and 50% RH.
Then, the central part of the heat seal part of the propylene-based resin sheet was cut out in the flow direction, and a section having a thickness of 20 μm was obtained in the cross section in the flow direction with a microtome. The section was observed with an optical microscope, and the thickness of the heat-sealed portion and the portion not heat-sealed was measured. The shape retention rate is expressed by the following formula.
Shape retention rate (%) = heat seal portion thickness ÷ thickness of non-heat sealed portion × 100
A sheet having a high shape retention rate has a sheet thickness, so that the sheet strength is also maintained, and is a good heat-sealed shape that is difficult to break as a package. When the shape retention is 72% or more, thinning of the heat seal portion is suppressed and the strength is excellent, 75% or more is preferable, and 77% or more is particularly preferable.

3. Resin used (1) Propylene resin composition (A)
A propylene-based resin composition PP (A-1) obtained by sequential polymerization according to the following production example (A-1) and a propylene-based resin composition PP (A-2) obtained by blending were used.

[Production Example (A-1): Production of PP (A-1)]
(I) Preparation of prepolymerized catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (trade name “Benclay SL” manufactured by Mizusawa Chemical Co., Ltd., average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and the temperature was maintained for 6.5 hours. Maintained. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(Preparation of catalyst)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was thoroughly replaced with nitrogen. 200 g of dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry.
Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 187 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(Prepolymerization / washing)
Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5,600 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 5,600 ml of the supernatant was removed. It was. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mM / L, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the presence in the supernatant with respect to the charged amount The amount was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
Using this prepolymerized catalyst, a propylene-based resin composition was produced according to the following procedure.

(Ii) First polymerization step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. While stirring at a rotation speed of 30 rpm in the presence of a polypropylene powder bed, 0.568 g / hr of the prepolymerized catalyst adjusted by the above method (as the amount of solid catalyst excluding the prepolymerized powder) in the upstream part of the reactor, Triisobutylaluminum was continuously fed at 15.0 mmol / hr. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the reactor gas phase is 0.07, and the hydrogen concentration is 100 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of the polymer extracted when the steady state was reached was 10.0 kg / hr.
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the MFR was 6.0 g / 10 min and the ethylene content was 2.2 wt%.

(Iii) Second polymerization step The propylene-ethylene copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. While stirring at a rotational speed of 25 rpm, the temperature of the reactor is maintained at 70 ° C., the pressure is maintained at 2.0 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.453, and the hydrogen concentration is 330 ppm. A monomer mixed gas was continuously passed through the reactor to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the polymerization reaction amount in the second polymerization step was controlled. The activity was 31.429 kg / g-catalyst.
Various analysis results of the propylene-based resin composition PP (A-1) thus obtained are shown in Table 3 below.
FIG. 1 is a graph showing a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) of a water-cooled inflation sheet of PP (A-1), with a single peak at 0 ° C. or lower. You can see that

(Granulation)
Furthermore, 0.05 parts by weight of the following antioxidant 1 and 0.05 parts by weight of the following antioxidant 2 are added to 100 parts by weight of the obtained propylene resin PP (A-1), and the mixture is sufficiently stirred and mixed. In a PCM twin screw extruder manufactured by Ikegai Manufacturing Co., Ltd. with a screw diameter of 30 mm, the melted resin extruded from the strand die was melted and kneaded in a cooling water tank at a screw rotation speed of 200 rpm, a discharge rate of 10 kg / hr, and an extruder temperature of 200 ° C. The polymer was taken up while being cooled and solidified, and the strand was cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter to obtain a propylene-based resin composition PP (A-1).
Antioxidant 1:
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (trade name “Irganox 1010” manufactured by BASF Japan Ltd.)
Antioxidant 2:
Tris (2,4-di-t-butylphenyl) phosphite (trade name “IRGAFOS 168” manufactured by BASF Japan Ltd.)

[Production Example (A-2): Preparation of PP (A-2)]
As component (A1), propylene-ethylene random copolymer “WINTEC WFW4M” (trade name, manufactured by Nippon Polypro Co., Ltd., MFR7, melting point: 135 ° C.) 56 wt% produced by metallocene catalyst, and as component (A2), metallocene catalyst A propylene-ethylene random copolymer “VISTAMAXX 3000” (trade name, manufactured by ExxonMobil Chemical Co., MFR8, ethylene content: 11 wt%) 44 wt% produced by the above method was kneaded with a twin screw extruder.
Various analysis results of the propylene resin composition PP (A-2) thus obtained are shown in Table 3 below.

(2) Reformer (B)
The ethylene-α-olefin copolymer PE (B-1) obtained in the following Production Example (B-1) was used.
(Production Example B-1)
A copolymer of ethylene and hexene-1 was prepared.
The catalyst was prepared by the method described in “Preparation of catalyst system” in the examples of JP-T-7-508545. That is, to the complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl 2.0 mmol, tripentafluorophenyl boron was added in an equimolar amount to the above complex, and diluted to 10 liters with toluene. Thus, a catalyst solution was prepared.
A mixture of ethylene and 1-hexene was supplied to a stirred autoclave type continuous reactor having an internal volume of 1.5 liter so that the composition of 1-hexene was 73% by weight, and the pressure in the reactor was maintained at 130 MPa. The reaction was performed at 127 ° C. The polymer production per hour was about 2.5 kg.
After the reaction was completed, various analyzes of the obtained polymer were performed. Various analysis results of the obtained ethylene-α-olefin copolymer PE (B-1) are shown in Table 4 below.

(3) Branched polypropylene resin (C)
A polypropylene resin PP (C-1) having a branch satisfying the scope of the present invention obtained in the following production example (C-1) and a branch not satisfying the condition (Ci) defined in the present invention shown below. The commercial product PP (C-2) not having was used.
PP (C-2):
Commercial product, product name "Novatec PP FY6H" manufactured by Nippon Polypro Co., Ltd.
Propylene homopolymer MFR: 1.9, melting point: 167 ° C., MT: 2.2

[Production Example (C-1): Production of PP (C-1)]
<Synthesis example 1 of catalyst component (M-1)>
Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (component [M-1] (complex 1) ):
(I) Synthesis of 4- (4-i-propylphenyl) indene To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) were added, and 90 g of cesium carbonate ( 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoindene and 5 g (4 mmol) of tetrakistriphenylphosphinopalladium were added in this order, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(Ii) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene, 7.2 ml of distilled water DMSO: 200 ml was added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(Iii) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 6.7 g (82 ml mol) of 2-methylfuran, DME: 100 ml And cooled to -70 ° C in a dry ice-methanol bath. To this, 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After the reaction solution was hydrolyzed with 50 ml of distilled water, a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 mg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in this order, and the mixture was heated at 80 ° C. The mixture was heated and reacted for 3 hours while removing low-boiling components.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene colorless liquid Yield 99%).

(Iv) Synthesis of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane In a 500 ml glass reaction vessel, 2- (2-methyl-5- Furyl) -4- (4-i-propylphenyl) indene (9.1 g, 29 mmol) and THF (200 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and 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, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column, and dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane pale 8.6 g (88% yield) of a yellow solid was obtained.

(V) Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium In a 500 ml glass reaction vessel, 8.6 g (13 mmol) of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane and 300 ml of diethyl ether were added, and -70 ° C. in a dry ice-methanol bath. Until cooled. Thereto was added dropwise 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with dichloromethane-hexane, and dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl]. }] 7.6 g (yield 65%) of a hafnium racemate as yellow crystals was obtained.

The identified value by ^{1 H-NMR} of the obtained racemates are described below.
¹ H-NMR (C6D6) identification result:
Racemate: δ 0.95 (s, 6H), δ 1.10 (d, 12H), δ 2.08 (s, 6H), δ 2.67 (m, 2H), δ 5.80 (d, 2H), δ6. 37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 (s, 2H), δ 7.30 (d, 2H) ), Δ 7.83 (d, 4H).

<Synthesis example 2 of catalyst component (M-2)>
rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (synthesis of component [M-2] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. It carried out like.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchanged layered silicate In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then montmorillonite (trade name “Benley SL” manufactured by Mizusawa Chemical Co., Ltd.), 4L) (average particle size 19 μm) was added. The slurry was heated at 90 ° C. for 210 minutes. The reaction slurry was filtered after adding 4,000 g of distilled water to obtain 810 g of a cake-like solid.
Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the cake solid was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, further washing with distilled water to pH 5-6, and filtration. As a result, 760 g of a cake-like solid was obtained.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed and further dried at 200 ° C. for 2 hours under reduced pressure to obtain 220 g of chemically treated montmorillonite.
The composition of this chemically treated montmorillonite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated montmorillonite obtained above was added, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was 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), complex 1 of the catalyst component [M-1] prepared in Synthesis Example 1 of the catalyst component (M-1), rac-dichloro [1,1′-dimethylsilylene] Bis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) was dissolved in toluene (42 mL) (solution 1), and another flask ( In a volume of 200 mL), the catalyst component [M-2] complex 2 prepared in Synthesis Example 2 of the catalyst component (M-2), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl- 4- (4-Chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) was dissolved in toluene (18 mL) (Solution 2).

Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the previously chemically treated montmorillonite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
Thereafter, 338 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 the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (12 mmol: 17.0 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 1 hour to obtain 56.4 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.82.
Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

<Polymerization>
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. Hydrogen 7.3NL (0.65 g) and triisobutylaluminum (0.12 mol: 0.47 L of heptane solution with a concentration of 50 g / L) were added thereto, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization.
The obtained polymer was dried at 90 ° C. under a nitrogen stream for 1 hour to obtain 18.2 kg of a propylene polymer (hereinafter referred to as PP (C-1)).
The catalytic activity was 7600 (g-PP / g-cat).

Tetrakis [methylene-3- (3 ′, 5′-di-), which is a phenolic antioxidant, with respect to 100 parts by weight of the propylene-based resin PP (C-1) produced in the above production example (C-1). t-butyl-4′-hydroxyphenyl) propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.125 parts by weight, tris (2,4-di-) as a phosphite antioxidant t-Butylphenyl) phosphite (trade name “IRGAFOS 168”, manufactured by BASF Japan Ltd.) 0.125 parts by weight is blended and mixed at room temperature for 3 minutes using a high-speed stirring mixer (Henschel mixer, trade name). After that, melt-kneading was performed with a twin-screw extruder to obtain polypropylene PP (C) pellets PP (C-1).
For the twin screw extruder, KZW-25 manufactured by Technobel was used, the screw rotation speed was 400 RPM, and the kneading temperature was 80, 160, 210, 230 from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). did.
Various analyzes of the obtained polymer were performed. Table 5 shows the analysis results.

The other analysis results of PP (C-1) are as follows.
CXS: 0.1 wt%
mm: 98.0%
Mw / Mn: 4.8
Mz / Mw: 3.7
Branch index g ′ when Mabs is 1 million: 0.88

(4) Resin composition for outer layer (Y)
The following outer layer resin composition (Y-1) was prepared and used using a commercially available propylene-based resin or the like.
Outer layer resin composition (Y-1):
As the propylene-based resin (D-1), a commercially available product name “Novatec PP MA3” (propylene homopolymer, MFR: 11 g / 10 min, melting point 163 ° C.) manufactured by Nippon Polypro Co., Ltd. is used. A resin composition comprising 70 wt%, 21 wt% of the propylene resin composition of PP (A-1) and 9 wt% of the ethylene-α-olefin copolymer of PE (B-1).

(5) Innermost layer resin composition (Z)
The following inner layer resin composition (Z-1) was prepared and used using a commercially available propylene-based resin or the like.
Inner layer resin composition (Z-1):
The PP (A-1) propylene-based resin 74 wt%, the PE (B-1) ethylene-α-olefin copolymer 25 wt%, and a commercial product “Novatech PP MA3” (Propylene) manufactured by Nippon Polypro Co., Ltd. A resin composition comprising 1 wt% of a homopolymer, g / 10 min, melting point 163 ° C.

[Examples 1 to 3]
The raw material pellets for each layer listed in Table 6 below were blended at the ratios shown in Table 6 and dry blended, and then melt-kneaded with a twin-screw extruder (Technobel KZW-25) and pellets. Got. A single screw extruder with a diameter of 30 mm was used as the inner layer extruder, a single screw extruder with a diameter of 18 mm was used as the outer layer and innermost layer extruder, and a set temperature of 200 from a circular die with a mandrel diameter of 50 mm and a lip width of 1.0 mm. Extruded at 0 ° C. and water-cooled, water-cooled inflation molding was performed at a speed of 3 m / min so as to have a folding width of 90 mm, and a cylindrical molded body having a total thickness of 200 μm consisting of the layer configuration shown in Table 6 was obtained. It was.
Next, after the cylindrical molded body made of the obtained laminated sheet is heat-treated by the above-described method, it is held for 24 hours or more in an atmosphere of 23 ° C. and 50% RH, and then the physical properties of the laminated sheet are evaluated. did. The evaluation results are shown in Table 6.
The laminated sheet satisfying the configuration of the present invention was excellent in transparency, flexibility, heat resistance, impact resistance, and appearance.

[Comparative Example 1]
A laminated sheet was obtained in the same manner as in Example 1 except that the components listed in Table 6 were used. The evaluation results are shown in Table 6.
In Comparative Example 1, since the MT of the component (C) was low, the die swell and the shape retention were inferior.

  The sheet molding resin composition of the present invention is excellent in moldability, and further, the propylene-based resin sheet using the resin composition has transparency, flexibility, heat resistance, low temperature impact resistance, and suitability for secondary processing. It is excellent, and the heat-treatment package using the same is extremely useful for infusion bags and retort packaging.

Claims (5)

Propylene-based resin composition (A) satisfying the following (Ai) to (A-ii) (1) to 98 wt%, modifier (B) satisfying the following (Bi) (1) to 50 wt%, and (C- A resin composition for sheet molding comprising a propylene-based resin composition (X) containing 1 to 50 wt% (provided that A + B + C = 100 wt%) of a polypropylene resin (C) having a branched structure satisfying i).
Propylene resin composition (A):
(Ai) The propylene-based resin composition (A) has a melting peak temperature (Tm (A1)) of 120 to 170 ° C., a propylene (co) polymer component (A1) of 30 to 70 wt%, and an α-olefin content. (E [A2]) contains 70-30 wt% of propylene-α-olefin random polymer component (A2) of 7-30 wt%.
(A-ii) Melt flow rate (MFR (A): 230 ° C., 2.16 kg) is in the range of 0.5 to 20 g / 10 min.
・ Modifier (B):
(Bi) At least one modifier selected from the group consisting of an ethylene-α-olefin copolymer and a styrene elastomer.
-Propylene resin (C) having a branched structure:
(Ci) Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7, or MT ≧ 15
Satisfy one of the following.   A propylene-based resin sheet comprising at least one layer formed of the resin composition for sheet molding according to claim 1.   The propylene-based resin sheet according to claim 2, wherein the thickness is 0.01 mm to 1.0 mm.   A package for heat treatment using the propylene-based resin sheet according to claim 2. Heat treatment package as claimed in claim 4 in which heat treatment for packaging is characterized in that it is a transfusion back grayed.

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