JP6213179B2 - Polypropylene resin composition for extrusion lamination and laminate - Google Patents

Description

  The present invention relates to a polypropylene-based resin composition for extrusion lamination and a laminate, and in particular, the neck-in is small, the lamination processability is excellent, and since the spreadability is high, the extrusion lamination processability at high speed is also excellent. The present invention relates to a polypropylene-based resin composition for extrusion lamination which is excellent in transparency and transparency of contents, and to a laminate which is excellent in drop bag resistance and impact resistance obtained by extrusion lamination.

  Conventionally, as food packaging materials, industrial materials, construction materials, etc., olefin resins such as ethylene resin and propylene resin are laminated on various resin films and sheets, various metal foils and plates, and substrates such as paper. Properties such as heat sealability, water vapor barrier property, waterproofness, rustproofness, etc., are mainly applied to the base material by extruding an olefin resin through the anchor coating agent. Then, an extrusion laminating method of forming a laminate is used.

  Polypropylene resins are superior to polyethylene resins in moisture resistance, gas permeability, oil resistance, heat resistance, stiffness of the waist and the like. On the other hand, polypropylene-based resin is a resin having a low melt tension because its molecular structure is linear and its molecular weight is not too large, and it is referred to as a neck-in in the extrusion lamination method, There is a large phenomenon that the width of the extruded film becomes smaller than the width, and there are processability problems such as surging (uneven thickness caused in the take-up direction or unstable phenomenon due to expansion and contraction of the edge portion) in lamination at high speed The

  In order to solve such problems, by blending low density polyethylene and amorphous ethylene-α-olefin copolymer with polypropylene, although the above problems of processability can be improved to some extent, it is made a laminated film At times, there were problems such as poor transparency and heat seal strength, and poor drop bag resistance and impact resistance (see, for example, Patent Documents 1 and 2).

Moreover, the technique which provides a melt tension to polypropylene resin itself as another method is developed. For example, Patent Document 3 discloses a technique for improving melt tension by introducing long chain branching into polypropylene by high energy ionizing radiation. Moreover, many techniques, such as patent documents 4-5, are similarly disclosed as a method of introduce | transducing a long chain branch to a polypropylene resin using organic peroxide.
However, the technology of introducing long-chain branching into polypropylene by high energy ionizing radiation irradiation or use of organic peroxides is, in the former, the cost increase at the time of production, yellowing problem, physical property change with time, and in the latter, organic There are problems such as contamination with decomposition products of peroxide, odor, yellowing, safety during production, etc., and a technique for producing high melt tension polypropylene by a method different from these has been desired.

In recent years, macromer copolymerization methods using a metallocene catalyst have been proposed. For example, a propylene macromer having a vinyl structure at an end is produced in a first polymerization step (macromer synthesis step) according to a specific complex and a specific polymerization condition, and then a specific catalyst in a second polymerization step (macromer copolymerization step). By copolymerizing with propylene under specific polymerization conditions, there is no high-order crosslinking, and the original chemical stability as polypropylene is not impaired, and the recyclability is also excellent, and gel for improving melt tension Have been devised (macromer copolymerization method) without concern of occurrence of (see, for example, Patent Documents 6 and 7).
However, in this method, it is necessary to polymerize at a relatively high temperature and a low pressure with a specific complex in order to efficiently obtain the terminal vinyl structure necessary as a macromer in the former stage. Therefore, the formed macromer becomes a macromer having low molecular weight and low tacticity.

  A single-stage polymerization method has been devised which simultaneously performs a macromer synthesis step and a macromer copolymerization step with a specific complex catalyst, as opposed to the above-described multi-step polymerization method (see, for example, Patent Document 8). However, in this method, the amount of macromer formation and the amount of macromer copolymerization are not always sufficient, and the effect of improving the melt properties is at an insufficient level.

According to the technique disclosed by the present applicant in Patent Documents 9 and 10, by carrying out propylene polymerization by single-stage polymerization in the presence of a catalyst containing a plurality of specific metallocene catalyst components, a macromer copolymer is obtained Various problems of the prior art in law are solved, and it is possible to obtain a long chain branch-containing polypropylene resin having very high melt tension and good tensile viscosity characteristics.
However, when extruding and laminating a resin having high melt tension itself, the poor flowability in the extruder makes it easy to increase the load, making it difficult to raise the extrusion rate, and when extruding laminated film forming, the drawability for taking away becomes poor. There is a possibility that problems such as the productivity can not be improved, such as the molding speed can not be increased and the film appearance is deteriorated.

JP-A-59-75934 JP-A-8-259752 Japanese Patent Application Laid-Open No. 62-121704 JP-A-6-157666 WO 99/27007 JP 2001-525460 gazette Japanese Patent Application Laid-Open No. 10-338717 Japanese Patent Application Publication No. 2002-523575 JP, 2009-57542, A JP, 2009-275207, A

  SUMMARY OF THE INVENTION In view of the problems of the prior art, the object of the present invention is to obtain a laminate having a small neck-in, excellent extrusion lamination processability at high speed, and excellent drop bag resistance and impact resistance. It is an object of the present invention to provide a polypropylene resin composition and a laminate for extrusion lamination.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a propylene-based polymer having a strain hardening degree (λmax) of 1.1 or more in measurement of extensional viscosity and a specific propylene-ethylene block copolymer By combining a polymer, or a propylene-based polymer and a specific propylene-ethylene block copolymer, a resin composition having a λmax of 1.1 or more while maintaining the high melt tension of a polypropylene resin, Since the neck-in is small, the laminate processability is excellent, and the spreadability is high, the extrusion laminate processability at high speed is also excellent, and the obtained laminate is excellent in the anti-fall bag resistance and the impact resistance. The present invention has been completed.
The present invention provides the following polypropylene-based resin composition and laminate for extrusion lamination.

[1] A propylene-based polymer (X) 3 which contains ethylene and / or 1-butene as a total amount of 10.0 mol% or less as a comonomer and has a strain hardening degree (λmax) of 1.1 or more in measurement of elongational viscosity It is characterized in that it is composed of 1 to 99% by weight, and 1 to 97% by weight of a propylene-ethylene block copolymer (Y) consisting of a propylene-based polymer component (A) and a propylene-ethylene random copolymer component (B). Polypropylene resin composition for extrusion lamination.
[2] 3 to 99% by weight of a propylene-based polymer (X) containing 10.0 mol% or less of ethylene and / or 1-butene as a total amount as a comonomer, a propylene-based polymer component (A) and propylene-ethylene random It is characterized by comprising 1 to 97% by weight of a propylene-ethylene block copolymer (Y) consisting of the copolymer component (B), and having a strain hardening degree (λmax) of 1.1 or more in measurement of extensional viscosity Polypropylene resin composition for extrusion lamination.
[3] The polypropylene-based resin composition for extrusion lamination as described in the above [1] or [2], wherein the propylene-based polymer (X) satisfies the requirements defined in the following (i) to (iv).
(I) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
(Ii) In a molecular weight distribution curve obtained by GPC, the ratio of components having a molecular weight of 2,000,000 or more is 0.4% by weight or more and less than 10% by weight based on the total amount.
(Iii) In the temperature rising elution fractionation (TREF) with ortho-dichlorobenzene (ODCB), the component eluting at a temperature of 40 ° C. or less is 3.0 wt% or less.
(Iv) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more.

[4] The polypropylene-based resin composition for extrusion lamination according to any one of the above [1] to [3], further characterized in that the propylene-based polymer (X) satisfies the requirements defined in the following (v): object.
(V) ME (memory effect) and MFR (melt flow rate: 230 ° C., 2.16 kg load) satisfy the following equation.
(ME) − − 0.26 × log (MFR) + 1.9
[In the equation, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and 1.00 mm in diameter, sets the temperature in the cylinder to 190 ° C, applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate at that time is divided by the orifice diameter. ]
[5] The polypropylene-based resin composition for extrusion lamination according to any one of the above [1] to [4], wherein the propylene-based polymer (X) further satisfies the requirements defined in the following (vi): object.
(Vi) in the molecular weight distribution curve obtained by GPC, the molecular weight of the common logarithm of Tp, a peak height of 50% of the height a position molecular weight logarithm and _{L 50} and _H 50 _{(L 50} corresponding to the peak position Tp lower molecular weight _{side, H 50} is a high molecular weight side) than Tp, alpha and beta, respectively α ₌ H 50 -Tp, when defining the _{β = Tp-L 50, α} / β is larger than 0.9, 2 Less than 0.
[6] The polypropylene-based resin composition for extrusion lamination according to any one of the above-mentioned [1] to [5], wherein the propylene-based polymer (X) further satisfies the requirements defined in the following (vii): object.
(Vii) MFR is 0.1 g / 10 minutes or more and 30 g / 10 minutes or less.

[7]
The polypropylene resin composition for extrusion lamination according to any one of the above [1] to [6], wherein the MFR of the propylene-ethylene block copolymer (Y) is 1 to 50 g / 10 min.
[8] The propylene-ethylene block copolymer (Y) is a propylene-ethylene block copolymer satisfying the following conditions (viii) to (x): [1] to [7] The polypropylene-based resin composition for extrusion lamination according to any one of the above.
(Viii) The melting peak temperature Tm (A) of the propylene polymer component (A) is 150 to 165 ° C.
(Ix) The ratio [W (B)] of the propylene-ethylene random copolymer component (B) to the total amount of the propylene-ethylene block copolymer (Y) is 10 to 50% by weight.
(X) The ethylene content [E (B)] of the propylene-ethylene block copolymer component (B) is 10 to 85% by weight.
[9] The propylene-ethylene block copolymer (Y) is a propylene-ethylene block copolymer polymerized using a metallocene catalyst, any one of the above-mentioned [1] to [8] The polypropylene resin composition for extrusion lamination as described in 4.
[10] A laminate obtained by melt extruding and laminating the polypropylene resin composition according to any one of the above [1] to [9] on a substrate.
[11]
A propylene-based polymer (X) for extrusion lamination according to the above [1] or [2], which satisfies the requirements (i) to (vii) according to the above [3] to [6].

  The polypropylene-based resin composition for extrusion lamination of the present invention has a small neck-in, is excellent in laminateability, and has a high spreadability, so is excellent in extrusion laminateability at high speed. And the obtained laminate is excellent in drop bag resistance and excellent in impact resistance.

FIG. 1 is a graph showing an example of a molecular weight distribution curve in GPC.

  Hereinafter, the embodiments of the present invention will be described in detail, but the description of the configuration requirements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents.

The polypropylene-based resin composition for extrusion lamination of the present invention contains ethylene and / or 1-butene in a total amount of 10.0 mol% or less as a comonomer and has a strain hardening degree (λmax) of 1.1 or more in measurement of elongational viscosity A propylene-ethylene block copolymer (Y) 1-1 comprising 3 to 99% by weight of the propylene-based polymer (X), the propylene-based polymer component (A) and the propylene-ethylene random copolymer component (B) It is characterized by comprising 97% by weight.
The polypropylene-based resin composition for extrusion lamination according to the present invention comprises 3 to 99% by weight of a propylene-based polymer (X) containing not more than 10.0 mol% of ethylene and / or 1-butene as a total amount as a comonomer 1 to 97% by weight of a propylene-ethylene block copolymer (Y) comprising a base polymer component (A) and a propylene-ethylene random copolymer component (B), and a strain hardening degree (λmax) in measurement of elongational viscosity Is 1.1 or more.

[Propylene-based polymer (X)]
The propylene-based polymer (X) used in the present invention contains ethylene and / or 1-butene in a total amount of 10.0 mol% or less as a comonomer, preferably a strain hardening degree (λmax) of 1 in measurement of elongational viscosity It is a long chain branched type propylene polymer which is .1 or more.
Each of the above-mentioned properties and the method for producing the propylene-based polymer (X) will be specifically described below.

[Comonomer of propylene polymer (X)]
The propylene-based polymer (X) used in the present invention may contain ethylene and / or 1-butene in a total amount of 10.0 mol% or less as a comonomer.
A so-called random copolymer obtained by copolymerizing a small amount of a comonomer with propylene has an advantage of improving flexibility and transparency because the crystallinity is lowered by the comonomer as compared with a propylene homopolymer, When the property is required, it is preferable to use ethylene or 1-butene as a random copolymer as a comonomer.

However, when a large amount of comonomer is present, the crystallinity is lowered too much, the melting point is lowered, and the heat resistance is deteriorated. In addition, when a comonomer is present during polymerization, chain transfer to the comonomer competes with the β-methyl elimination reaction, and the formation efficiency of the macromer decreases, resulting in a problem that the melt property is impaired.
Therefore, in order to obtain a propylene polymer (X) having good balance of flexibility, transparency, heat resistance, and melt properties, ethylene and / or 1-butene should be a random copolymer of 10 mol% or less. Is preferably 7.0 mol% or less, more preferably 5.0 mol% or less.

  Moreover, when ethylene and 1-butene are compared as a comonomer, even if it is the same mol% content, the direction of ethylene lowers crystallinity and the effect of reducing melting | fusing point is large. That is, when the comonomer is 1-butene, the comonomer content can be increased due to the melting point and heat resistance, as compared with ethylene.

Moreover, when 1-butene is used as a comonomer, compared with the case of ethylene, the fall of the melting | fusing physical property seen by distortion hardening degree ((lambda) max) is small by melting | fusing point balance. The reason is not necessarily clear, but the chain transfer rate to 1-butene is smaller compared to ethylene, so that in the case of 1-butene, the decrease in macromer formation efficiency is small even if the comonomer content is high It is estimated that.
Therefore, in addition to ethylene / propylene random copolymer, ethylene / 1-butene / propylene random copolymer, 1-butene / propylene random copolymer in which part or all of ethylene is changed to 1-butene It is preferable to do. In this case, it is preferable to use 10.0 mol% or less of 1-butene as a comonomer, preferably 7.0 mol% or less, and more preferably 5.0 mol% or less.
Also, comonomers other than ethylene and 1-butene, for example, 1-hexene and 3-methyl-1-pentene can be used as long as the physical properties described above are not impaired.
The ethylene content and 1-butene content are measured using ¹³ C-NMR and using ¹³ C-NMR spectra obtained by mm measurement described later.

[Strain hardening degree (λmax) in measurement of elongation viscosity]
The propylene-based polymer (X) of the present invention has a strain hardening degree (λmax) itself of 1.1 or more in measurement of extensional viscosity, or a resin composition with a propylene-ethylene block copolymer (Y) It is necessary that it is 1.1 or more as a thing.

The degree of strain hardening (λmax) is an index showing the strength at melting, and when this value is large, the effect of improving the melt tension is obtained. As a result, for example, draw resonance is less likely to occur during laminate molding.
Therefore, the strain curing degree of the propylene-based polymer (X) needs to be 1.1 or more, preferably 2.0 or more, more preferably 4.0 or more, and still more preferably 6.0 or more.
Alternatively, the strain curing degree of the resin composition of the propylene polymer (X) and the propylene-ethylene block copolymer (Y) needs to be 1.1 or more, preferably 1.2 or more, more preferably 1 .3 or more.
Further, the strain hardening degree is an index that represents the non-linearity of the extensional viscosity, and it is generally said that the larger the molecular entanglement, the larger the value. Molecular entanglement is influenced by the amount of branching, the length of the branched chain. Therefore, the degree of strain hardening increases as the amount of branching and the length of the branching increase.
At the present time, it is considered to be the most sensitive method for evaluating branching, and it is difficult to evaluate the branched structure directly by ¹³ C-NMR, so instead of that method, the strain hardening degree is branched It was used as an index.

Generally, in order to exhibit a high degree of strain hardening, a entanglement molecular weight of 7,000 or more of polypropylene is required as a branch length. It corresponds to about 400 or more when converted to the number of skeletal carbons. The framework carbon as used herein means all carbon atoms other than methyl carbon. The melt properties are considered to be further improved as the branch length becomes longer. It is believed that strain hardening is likely to be detected in the measurement of extensional viscosity even in the lower strain rate region, particularly when longer branched chains are introduced.
Therefore, the branched chain length of the propylene-based polymer (X) is preferably 500 or more carbon atoms in the skeleton (polypropylene molecular weight conversion: 11,000) or more, and more preferably 1,000 carbon atoms (polypropylene molecular weight conversion: 2.1) Or more, and more preferably a carbon number of 2000 skeletons (polypropylene molecular weight conversion: 42,000) or more.
The polypropylene molecular weight conversion value referred to here is strictly different from the molecular weight value measured by GPC, but approximates the number average molecular weight (Mn) measured by GPC.
Therefore, the branched chain length of the propylene-based polymer (X) is preferably 11,000 or more, more preferably 21,000 or more, still more preferably 4.2, in number average molecular weight (Mn) measured by GPC. It is considered to be replaced with over 10,000.

  Here, as a method of measuring the degree of strain hardening, the same value can be obtained in principle by any method as long as the uniaxial elongation viscosity can be measured. For example, for details of the measuring method and measuring instrument, refer to Polymer 42 (2001) Although there is a method described in (8) 8663, preferred measuring methods and measuring instruments include the following.

Measurement method 1:
Device: Rheometrics Ares
Fixture: TA Instruments Extentional Viscosity Fixture
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.

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

Calculation method:
Strain rate: The extensional viscosity in the case of 0.1 / sec is plotted on a double logarithmic graph with time t (second) on the horizontal axis and extensional viscosity _{E E} (Pa · second) on the vertical axis. The viscosity immediately before causing strain hardening on the bilogarithmic graph is approximated by a straight line, and the maximum value (ηmax) of the extension viscosity η _E until the strain amount reaches 4.0 is determined, and the approximate straight line up to that time Let the above viscosity be η lin.
The strain rate can be measured in the range of 0.001 / sec to 10.0 / sec, and the strain hardening degree changes depending on the strain rate. The strain rate dependency of the strain hardening degree is considered to change depending on the form and length of the introduced branch.

The strain hardening degree (λmax) in the measurement of the extensional viscosity of a propylene-based polymer is as large as 1.1 or more by controlling the selection of the two types of metallocene complexes constituting the catalyst used for propylene polymerization and the ratio thereof. can do. That is, one of the two types of metallocene complexes is apt to easily form a macromer, and the other is selected to easily incorporate a macromer into a polymer and to form a polymer of high molecular weight. At this time, λmax can be increased by increasing the amount of macromer by increasing the ratio of the macromer-forming complex. Further, λmax can be increased by selecting a copolymerizable complex as the copolymer complex.
Furthermore, by performing prepolymerization, the value of λmax can be increased by uniformly distributing long chain branching among polymer particles.
The reverse operation is performed to reduce the value of λmax.
Further, at the time of polymerization, when hydrogen is added, the amount of high molecular weight components relatively decreases in the polymer, and the number of branches per single chain decreases and λmax gradually decreases. In addition, when ethylene is added at the time of polymerization, the polymerization speed of the macromer relatively decreases, so that the number of branches decreases and the value of λmax decreases. Also, when other comonomers such as butene are used, the polymerization speed of the macromer relatively decreases to decrease the number of branches, and the value of λmax also decreases.
In other words, at the time of catalyst synthesis, appropriate amounts and ratios of two kinds of complexes are selected, prepolymerization is appropriately performed, hydrogen is used at the time of polymerization, molecular weight and molecular weight distribution are adjusted, and types of comonomer such as ethylene and butene It is possible to obtain a desired polymer of λmax by selecting the amount and the amount appropriately.

  The propylene-based polymer (X) preferably further has the following characteristics (i) to (vii).

(I) Molecular weight distribution measured by GPC (Mw / Mn)
The propylene-based polymer (X) has a weight-average molecular weight (Mw) to number-average molecular weight (Mn) ratio of 3.5 to 10.5 as measured by gel permeation chromatography (GPC). It is preferable that it is a range.
Mw / Mn is an index representing the spread of the molecular weight distribution, and the larger the value, the wider the molecular weight distribution. When the Mw / Mn is 3.5 or more, the distribution is optimum, so that the balance between melt spreadability and processability is good. Therefore, Mw / Mn is preferably 3.5 or more, more preferably a value larger than 4.0. More preferably, it is a value larger than 4.5. On the other hand, when Mw / Mn is 10.5 or less, the amount of unnecessary (low) molecular weight components is reduced, and a material having satisfactory physical properties is obtained. Therefore, Mw / Mn is preferably 10.5 or less, more preferably less than 8.0, and still more preferably less than 7.5.

  The average molecular weight and molecular weight distribution (Mw, Mn, Mw / Mn) measured by GPC of a propylene-based polymer change the temperature and pressure conditions of propylene polymerization or, as the most general method, a chain such as hydrogen The adjustment can be easily performed by the method of adding the transfer agent at the time of propylene polymerization. Furthermore, the type of metallocene complex to be used, and in the case of using two or more complexes, can be controlled by changing the ratio of the amounts.

(Ii) Ratio of components having a molecular weight (M) of 2,000,000 or more in the molecular weight distribution curve by GPC The propylene-based polymer (X) has a molecular weight (M) relative to the total amount of polymer in the molecular weight distribution curve obtained by GPC It is preferable that the ratio (W (2 million or more)) of the component of 2,000,000 or more is 0.4 weight% or more and less than 10 weight%.
The ratio of 2,000,000 or more (W (2,000,000 or more)) is an index indicating the ratio of a very high molecular weight component contained in the polymer. The ratio W (2,000,000 or more), which is the ratio of very high molecular weight components, has a molecular weight (M) of 2,000,000 (Log (M) = 6.) In the integrated molecular weight distribution curve (total amount normalized to 1) obtained by GPC. 3) The integral value up to the following is defined as a value subtracted from 1 as well known.

If the amount of high molecular weight component is insufficient, the melt tension and swell ratio will be small, so a component with a high molecular weight is required, and by containing a very small amount of a component with a very high molecular weight, the formability is improved efficiently Be done. It is believed that this very high molecular weight component contains branched components.
Accordingly, the propylene polymer (X) preferably has a W (2,000,000 or more) of 0.4% by weight or more, more preferably 1.0% by weight or more, and still more preferably 2.0% by weight It is above.
However, if the ratio of this component is too high, the fluidity will be deteriorated. Moreover, since it is a component with a very high molecular weight, a gel will be produced | generated and the problem of impairing an appearance arises. Moreover, when the ratio of this component is too high, it causes deterioration of melt spreadability.
Therefore, the propylene-based polymer (X) preferably has W (2,000,000 or more) less than 10% by weight, more preferably less than 6.0% by weight, and still more preferably less than 5.0% by weight.

  The ratio of the component having a molecular weight (M) of 2,000,000 or more in the molecular weight distribution curve of the propylene-based polymer (X) by GPC is a low molecular weight after selecting one capable of producing a high molecular weight polymer as the metallocene complex to be used. Adjustment can be easily performed by controlling the amount ratio to the metallocene complex to be produced on the side, the amount of hydrogen added at the time of propylene polymerization, and the polymerization temperature.

  The values of weight average molecular weight (Mw), Mw / Mn, α / β, and W (2,000,000 or more) defined above are all obtained by gel permeation chromatography (GPC), The details of the measuring method and measuring instrument are as follows.

Equipment: GPC (ALC / GPC, 150C) manufactured by Waters
Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD 806 M / S (three in series)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The preparation of the sample is performed by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and taking about 1 hour at 140 ° C. to dissolve the sample.
Moreover, conversion from the retention volume obtained by GPC measurement to molecular weight is performed using a calibration curve with standard polystyrene prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation.
Brand Name: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is generated by injecting 0.2 mL of a solution in ODCB (containing 0.5 mg / mL BHT), each at 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method.
The viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(Iii) Temperature rising elution fractionation (TREF) with ortho-dichlorobenzene (ODCB)
The propylene polymer (X) preferably has a component eluted at a temperature of 40 ° C. or less at 3.0 wt% or less in an elution curve obtained by temperature-rising elution fractionation (TREF) measurement.
The component that elutes at a temperature of 40 ° C. or less is a low crystalline component, and when the amount of this component is small, crystallinity is improved and strength is likely to be improved. Accordingly, the amount is preferably 3.0% by weight or less, more preferably 2.0% by weight or less, still more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. is there.

  Temperature-rising fractionation (TREF) of propylene-based polymer (X) with orthodichlorobenzene (ODCB) can be generally suppressed to a low level by using a metallocene complex, but the purity of the catalyst is kept at a certain level or higher. In addition to keeping, it is necessary not to make the method for producing the catalyst or the reaction conditions at the time of polymerization extremely high temperature nor to raise the ratio of organic aluminum to the metallocene complex too much.

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

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

(Iv) Isotactic triad fraction (mm) measured by ¹³ C-NMR
The propylene-based polymer (X) is preferably one having a stereoregularity in which the mm fraction of three propylene unit chains obtained by ¹³ C-NMR is 95% or more.
The mm fraction is the proportion of propylene unit triples in which the direction of the methyl branch in each propylene unit is the same in any propylene unit chain consisting of head-to-tail bonds in the polymer chain. The mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is isotactically controlled, and the higher the value, the higher the degree of control.
When the mm fraction is larger than this value, mechanical properties are improved. Therefore, the mm fraction is preferably 96% or more, more preferably 97% or more.
Moreover, the stereoregularity of a principal chain and a side chain is decided by the stereoregular ability which catalyst component [A-1] and [A-2] which are used by the manufacturing method of the propylene-type polymer mentioned later have. If the stereoregularity of the side chain is low, even if the crystallinity of the main chain is high, the overall crystallinity is lowered. Therefore, in order to be a polymer with higher rigidity, it is preferable that both the side chain and the main chain have high stereoregularity. As the value thereof, it is preferable that the main chain and the side chain have a mm fraction of 95% or more. More preferably, it is 96% or more, More preferably, it is 97% or more.

The isotactic triad fraction (mm) measured by ¹³ C-NMR of the propylene-based polymer can be easily adjusted by the selection of the metallocene complex to be used and the polymerization temperature.
In addition, the measuring method of the mm fraction of 3 units of propylene units by ¹³ C-NMR is as well known, and specifically according to the method described in Japanese Patent Application Laid-Open No. 2009-275207.

(V) Memory effect (ME)
In the propylene polymer (X), it is desirable that the memory effect (ME) satisfy the following formula (1).
(ME) − − 0.26 × log (MFR) + 1.9 (1)
[In the equation, ME is a melt indexer having an orifice length of 8.00 mm and a diameter of 1.00 mmφ, and a temperature in the cylinder is set to 190 ° C. to apply a load and an extrusion speed of 0.1 g / min At the same time, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate at that time is divided by the orifice diameter. ]

In the propylene polymer (X), the correlation between the memory effect (ME) as an index representing the proportion of the high molecular weight component in the polymer and the MFR as an index representing the average molecular weight of the polymer is the relationship of the above formula (1) Is preferred.
ME is an index indicating non-Newtonianity of a polymer, and a large ME indicates that a component having a long relaxation time is present in the polymer. That is, when ME is large at the same MFR, it means that the long-term relaxation component is distributed in the polymer.
Also, it is empirically known that ME has a first-order correlation with Log (MFR), and in general, the larger the molecular weight (that is, the smaller the MFR value), the larger the value of ME. .

The propylene-based polymer (X) has a branched component in the polymer chain, so the ME in MFR is larger than that of the conventionally known polymer, and the molding property is excellent when the amount of the long-term relaxation component is large. More preferably, it is preferable to satisfy the following formula (2) and further the following formula (3).
(ME) − − 0.26 × log (MFR) + 2.20 (2)
(ME) − − 0.26 × log (MFR) + 2.40 (3)

  As a measurement method of memory effect (ME), using a melt indexer manufactured by Takara Co., Ltd., a force is applied to push out an orifice diameter of 1.0 mm and a length of 8.0 mm at 190 ° C., and the extrusion speed is 0.1 g. At this time, the polymer extruded from the orifice is quenched in ethanol, and the value of the strand diameter at that time is divided by the orifice diameter.

  The memory effect (ME) of the propylene-based polymer (X) controls, for example, the selection and combination of the metallocene complexes described later and their ratio, and the prepolymerization conditions, which are used for the polymerization of the propylene-based polymer In some cases, adjustments can be made.

(Vi) Bias of spread of molecular weight distribution obtained from molecular weight distribution curve by GPC to high molecular weight side The propylene polymer (X) is a common logarithm of molecular weight corresponding to a peak position in the molecular weight distribution curve obtained by GPC Let L ₅₀ and H ₅₀ (L _{50 be} lower molecular weight than Tp, H _{50 be} higher molecular weight than Tp) be the common logarithm of the molecular weight at the position where Tp and 50% of the peak height be high. = _H 50 -Tp, when defining the _{β = Tp-L 50, α} / β is larger than 0.9, it is desirable that less than 2.0. Here, α / β is an index representing a bias toward the high molecular weight side of the spread of the molecular weight distribution.

The spread of the molecular weight distribution is indicated by a molecular weight distribution curve obtained by GPC. That is, a graph is created in which the relative differential mass of the molecule corresponding to the MW is plotted on the vertical axis with the common logarithm of the molecular weight (MW) as the horizontal axis.
In addition, the molecular weight (MW) said here is the molecular weight of each molecule which comprises a propylene homopolymer, Comprising: It differs from the weight average molecular weight (Mw) of a propylene homopolymer. FIG. 1 is a graph showing an example of a molecular weight distribution curve. Α and β are determined from the created graph. In the present invention, as described above, it is desirable that α / β be greater than 0.9 and less than 2.0.

In general, when homogeneous polymerization is carried out with a catalyst having a single active point, the molecular weight distribution is most likely the shape of the distribution. This most likely distribution of α / β is calculated to be 0.9.
Therefore, the molecular weight distribution of the propylene-based polymer (X) means that the molecular weight distribution of the propylene-based polymer (X) is further spread on the higher molecular weight side as compared with the molecular weight distribution of the polymer uniformly polymerized at a single active point.
If α / β is larger than 0.9, the amount of high molecular weight components will be relatively sufficient, and the melt tension will be large, and the formability will improve, so the molecular weight distribution is higher on the high molecular weight side than on the low molecular weight side It is important that it is even more widespread.
Accordingly, in the propylene polymer of the present invention, α / β is preferably greater than 0.9, more preferably 1.0 or more, and still more preferably 1.1 or more.

On the other hand, when α / β is less than 2.0, the amount of the high molecular weight component becomes appropriate, and the fluidity becomes good. In addition, so-called melt spreadability deterioration in which the melt fractures when stretched at a high speed during molding is avoided.
Therefore, it is preferable that alpha / beta is less than 2.0, as for a propylene polymer (X), More preferably, it is less than 1.7, More preferably, it is less than 1.6.
In the molecular weight distribution curve, two or more peaks may appear. In that case, the maximum peak can be replaced with the peak in the present invention. When two or more H ₅₀ appear, they can be replaced with the molecular weight at the highest molecular weight side. Similarly, when two or more L ₅₀ appear, they can be replaced with the molecular weight of the lowest molecular weight side.

  The bias to the high molecular weight side of the spread of the molecular weight distribution obtained from the molecular weight distribution curve by GPC of the propylene-based polymer (X) was selected from those which can produce a high molecular weight polymer as one of the two metallocene complexes used. In addition, adjustment can be easily performed by controlling the amount of hydrogenation added during polymerization. It can also be adjusted by changing the ratio of the two metallocene complexes used.

(Vii) Melt flow rate (MFR)
The propylene-based polymer (X) preferably has a melt flow rate (MFR) of 0.1 g / 10 minutes or more and 30 g / 10 minutes or less measured at a temperature of 230 ° C. and a load of 2.16 kg.
MFR is an index showing fluidity, and as the molecular weight of the polymer increases, this value decreases, while as the molecular weight decreases, this value increases. In general, when this value is small, the flowability is deteriorated and various moldings can not be performed. Therefore, the MFR is preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more, and still more preferably 0.3 g / 10 min or more.
In general, when this value is large, although the fluidity is improved, the molecular weight may be too small, which may cause deterioration of mechanical properties such as a decrease in impact strength when formed into a molded body. Therefore, the MFR is preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less, and still more preferably 15 g / 10 min or less.

  Melt flow rate (MFR) is the test condition according to JIS K 6921-2 "Plastic-material for molding and extrusion (PP)-Part 2: How to make test pieces and how to find properties". : A value measured at 230 ° C. and a load of 2.16 kgf.

The melt flow rate (MFR) of the propylene-based polymer (X) is changed by changing the temperature or pressure conditions of propylene polymerization, or adding the chain transfer agent such as hydrogen at the time of polymerization as the most general method It can be easily adjusted.
Moreover, adjustment by organic peroxide degradation can also be performed after polymerizing a propylene-based polymer (X), or organic peroxide after blending a propylene-based polymer (X) and a propylene-based resin (Y) It is also possible to make adjustments by degradation. The organic peroxide used at that time is benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3. 1,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) Oxy) valerate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, 1,3-bis (t-butylperoxyisopropyl) benzene, α, α′-bis (t-butylperoxyi) Propyl) benzene, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, di-t-butyl-dipperoxy phthalate, t-butyl peroxymaleic acid, t-butyl peroxy isopropyl carbonate Carbonate etc. are mentioned.

  These can be used combining not only 1 type but 2 types or more. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 1,3 Particularly preferred is -bis (t-butylperoxyisopropyl) benzene or α, α'-bis (t-butylperoxyisopropyl) benzene.

  The decomposition method uses 0.005 to 0.1 parts by weight of an organic peroxide per 100 parts by weight of the resin composition, and heats both at a temperature higher than the melting temperature of the resin, for example, 180 to 300 ° C. Kneading may be employed, and any method may be adopted as the method, but it is particularly preferable to carry out in an extruder. Before heat-kneading both of them so that the organic peroxide is uniformly dispersed in the crystalline polypropylene resin, the both are sufficiently mixed in advance using a mixer such as a Henschel mixer (trade name) or a ribbon blender. It is also good. Furthermore, in order to improve the dispersibility of the organic peroxide, a mixture of the organic peroxide in a suitable medium can also be used.

Moreover, although the adjustment method regarding the molecular weight of a propylene polymer such as MFR, Mw / Mn, α / β and the ratio of components having a molecular weight (M) of 2,000,000 or more has been described so far, for example, common control method The control of the amount of hydrogen can be mentioned as When the amount of hydrogen is increased, the MFR of the propylene-based polymer is increased, and the ratio of components having a Mn / Mn, α / β, and molecular weight (M) of 2,000,000 or more tends to decrease.
On the other hand, MFR can also be raised by a method of raising the polymerization temperature or lowering the monomer partial pressure, in which case the ratio of components having a molecular weight (M) of 2,000,000 or more decreases, but with Mn / Mn α / β is not significantly affected. Further, the ratio of components having a molecular weight (M) of 2,000,000 or more to MFR can be controlled by changing the amount and type of the metallocene complex that forms the high molecular weight side. Thus, control of these specifications is possible by changing the catalyst and polymerization conditions to be used.

[Method for producing propylene-based polymer (X)]
As a method for producing a propylene-based polymer (X), any method can be obtained as long as it is a long-chain branched propylene-based polymer excellent in the balance between physical properties and processability, with the above-mentioned melt spreadability and melt tension controlled. Although it is not particularly limited, for example, as a method of introducing a controlled branched component, a method using a plurality of complexes as described below can be mentioned.

That is, it is a method of producing the above-mentioned long chain branched propylene polymer,
As a propylene polymerization catalyst, the following catalyst components (A), (B) and (C) are used, The manufacturing method of the propylene polymer characterized by the above-mentioned is mentioned.
(A): From the component [A-1] which is a compound represented by the following general formula (a1), and at least one from the component [A-2] which is a compound represented by the general formula (a2) Type, two or more selected transition metal compounds of Group 4 of periodic table Component [A-1]: compound represented by General Formula (a1) Component [A-2]: represented by General Formula (a2) Compound (B): ion exchangeable layered silicate (C): organoaluminum compound

The catalyst components (A), (B) and (C) will be described in detail below.
(1) Catalyst component (A)
(I) Component [A-1]: Compound Represented by General Formula (a1)

[In general formula (a1), each of R ¹¹ and R ¹² independently represents a nitrogen- or oxygen-sulfur-containing heterocyclic group having 4 to 16 carbon atoms. In addition, each of R ¹³ and R ¹⁴ is independently an aryl having 6 to 16 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or a plurality of hetero elements selected therefrom. And a heterocyclic group containing 6 to 16 carbon atoms, nitrogen or oxygen and sulfur. Furthermore, X ¹¹ and Y ¹¹ 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, a halogenation having 1 to 20 carbon atoms 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 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, Represents a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The nitrogen- or oxygen-sulfur-containing heterocyclic group 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, a substituted Preferred is a substituted 2-furfuryl group, more preferably a substituted 2-furyl group.
In addition, as a substituent of the substituted 2-furyl group, the substituted 2-thienyl group, and the substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group or a propyl group, A fluorine atom, a halogen atom such as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a trialkylsilyl group can be mentioned. Among these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Furthermore, as R ¹¹ and R ¹² , particularly preferred is a 2- (5-methyl) -furyl group. Further, it is preferable that R ¹¹ and R ¹² be identical to each other.

As the above-mentioned R ¹³ and R ¹⁴ , an aryl group having 6 to 16 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or a plurality of hetero elements selected therefrom, One or more hydrocarbon groups having 1 to 6 carbon atoms, silicon containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms It may have a containing hydrocarbon group as a substituent.
Preferably, at least one of R ¹³ and R ¹⁴ is a phenyl group, 4-i-propylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di-t-butyl It is a phenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group or phenanthryl group, more preferably phenyl group, 4-i-propylphenyl group, 4-t-butylphenyl group, 4-chlorophenyl group . It is also preferred that R ¹³ and R ¹⁴ be identical to each other.

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

In the general formula (a1), Q ¹¹ is a silylene having a carbon number of 1 to 20, and a divalent hydrocarbon group having a carbon number of 1 to 20 and a hydrocarbon group having a carbon number of 1 to 20 which links two five-membered rings Indicates either a group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ¹¹ include alkylene groups such as methylene, methyl methylene, dimethyl methylene, 1,2-ethylene and the like; aryl alkylene groups such as diphenyl methylene; silylene groups; methyl silylene, dimethyl silylene, diethyl silylene, di Alkyl silylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; An alkyl oligosilylene group such as tetramethyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-described silylene group having a hydrocarbon group having 1 to 20 carbon atoms is substituted with germanium; (alkyl) (aryl) Germylene group; Arylgermylene Groups can be mentioned. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

Among the compounds represented by the above general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylene bis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (2-thienyl) -4-phenyl] -Indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-diphenylsilylene bis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylgermylene bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} Hafnium, dichloro [1,1′-dimethylgermylene bis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, diqu [1,1'-dimethylsilylene bis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {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'-dimethylsilylene bis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylene bis {2- (5-methyl-2-furyl) -4-4 Henyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5 -Methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4-fluoro) Phenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1 1′-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, Chloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis { 2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (2-furyl) -4- (2-naphthyl) -indenyl} Hafnium, dichloro [1,1′-dimethylsilylene bis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (2) -Furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (1-naphthy] ) -Indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'- Dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) ) -4- (9-Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl} Hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1] 1'-dimethylsilylene bis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-) t-Butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-) 2-Furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl] -Indenyl}] hafnium, etc. can be mentioned.

  Among these, dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel is more preferable. Mylene bis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4) 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 1′-Dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, dichloro [1,1 ′ Dimethylsilylenebis {2- (5-methyl-2-furyl)-4-(4-t-butylphenyl) - indenyl}] hafnium,.

  Also particularly preferred are dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis { 2- (5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-] (4-i-Propylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} Hafnium.

  Also particularly preferred are dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis { 2- (5-Methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2- (5-methyl-2-furyl) -4-] (4-t-Butylphenyl) -indenyl}] hafnium.

(Ii) Component [A-2]: Compound Represented by General Formula (a2)

[In general formula (a2), each of R ²¹ and R ²² is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus or a plurality of hetero elements selected therefrom. 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, 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, the carbon number It represents a silylene group or 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 thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like, with preference given to methyl , Ethyl, n-propyl.

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

The above X ²¹ and Y ²¹ are auxiliary ligands, which react with the cocatalyst of component (B) to form an active metallocene having olefin polymerization ability. Therefore, X ²¹ and Y ²¹ are not limited in the type of ligand as long as this object is achieved, and each of X ²¹ and Y ²¹ is independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, carbon It shows an alkoxy group of 1 to 20, an alkylamide group of 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group of 1 to 20 carbon atoms or a silicon-containing hydrocarbon group of 1 to 20 carbon atoms.

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

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

The following can be mentioned as non-limiting examples of the metallocene compound represented by the above general formula (a2).
However, in the following, only representative exemplary compounds have been described avoiding many complicated examples. Also, although a compound in which the central metal is hafnium is described, it is obvious that similar zirconium compounds can also be used, and various ligands, crosslinking groups or auxiliary ligands can optionally be used.
Dichloro {1,1′-dimethylsilylene bis (2-methyl-4-phenyl-4-hydroazulenyl)} hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis { 2-Methyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-Hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-methyl-4- (3-methy) -4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium Dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl] -4- (1-Naphthyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-methyl-4- (2-naphthyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 1'-Dimethylsilylene bis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazle Nyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis { 2-Methyl-4- (2-chloro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (9-phenanthryl) -4-hydroazulenyl} Hafnium, dichloro [1,1′-dimethylsilylene bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-n-propyl-] 4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1 1′-Dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-ethyl-4- 4 (3-Methyl-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylgermylene bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl} Hafnium, dichloro [1,1′-dimethylgermylene bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene- 9,9-Diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ' -Dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] 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-Hydroazulenyl}] hafnium, and the like.

  Among these, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazulenyl}] With dichloro [1,1 '-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium, is there.

  Also particularly preferably, dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylene bis {2-ethyl] -4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1'-dimethylsilylene bis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-] Hydroazulenyl}] hafnium, dichloro [1,1 '-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] Hafnium.

(2) Catalyst component (B)
Next, the catalyst component (B) is an ion exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter simply referred to simply as silicates) used as raw materials have their surfaces constituted by ionic bonds etc. stacked in parallel by bonding force. It is a silicate compound having a crystal structure and having exchangeable ions contained therein. Most silicates are naturally produced mainly as a main component of clay minerals, and thus they often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. May be. Depending on the type, amount, particle size, crystallinity, and dispersion state of such contaminants, it may be preferable to pure silicate or more, and such a complex is also included in component (B).
Here, the raw material refers to a silicate before the chemical treatment of the present invention described later. Moreover, the silicate to be used is not limited to a naturally occurring one, and may be an artificially synthesized product. You may include them.

Specific examples of the silicate include, for example, the following layered silicates described in "Clay Mineralogical Science" by Haruo Shiramizu, Asakura Shoten (1995).
That is, smectites such as montmorillonite, saudikonite, beidellite, nontronite, saponite, hectorite, and stevensite, vermiculites such as vermiculite, micas such as mica, illite, sericite, sea-greenstone, attapulgite, sepiolite, palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

  The silicate used as the raw material is preferably a silicate having a 2: 1-type structure as the main component, more preferably a smectite group, and montmorillonite is particularly preferable. The type of interlayer cation is not particularly limited, but in view of availability as an industrial raw material relatively easily and inexpensively, a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable.

(Ii) Chemical Treatment of Ion-Exchanged Layered Silicate The ion-exchanged layered silicate of the catalyst component (B) can be used as it is without treatment, but chemical treatment is preferably carried out. Here, the chemical treatment of the ion exchange layered silicate may be either surface treatment for removing impurities attached to the surface or treatment for affecting the structure of clay, and specifically, acid treatment Treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned.

<Acid treatment>:
The acid treatment removes impurities on the surface and can elute part or all of cations such as Al, Fe, Mg, and the like having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid.
The salts (described in the next section) and the acid used for the treatment may be two or more. The conditions for treating with salts and acids are not particularly limited, but usually the concentrations of salts and acids are 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. It is preferable to carry out the reaction under such conditions as to elute at least a part of the substance constituting at least one compound selected from the group consisting of ion exchange layered silicates. Also, salts and acids are generally used in 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>:
Ions dissociated from the salts shown below by at least 40%, preferably at least 60% of the exchangeable Group 1 metal cations contained in the ion exchange layered silicate before being treated with the salts It is preferable to replace it.
The salts used in the salt treatment for the purpose of such ion exchange are a group consisting of a cation containing at least one atom selected from the group consisting of Group 1-14 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, more preferably a cation containing at least one atom selected from the group consisting of group 2-14 atoms and Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), O (SO ₄ ), And 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 It is a compound consisting of

Specific examples of such salts include 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.

_{Further, 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 2, Fe (OOCCH 3) 2} , Fe (CH 3 COCHCOCH 3) 3, FeCO 3, Fe (NO 3) 3, Fe (ClO 4) 3, FePO 4, FeSO 4, Fe 2 (SO 4) 3, FeF3 , FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

_{Furthermore, 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 And 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 the acid and salt treatments, the following alkali treatments and organic matter treatments may be carried out, if necessary. Examples of the treating agent used in the alkaline treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic substance treatment>:
Moreover, trimethyl ammonium, triethyl ammonium, N, N- dimethyl anilinium, triphenyl phosphonium etc. are mentioned as an example of the organic processing agent used for organic substance processing.
Further, as the anion constituting the organic substance treating agent, in addition to the anion exemplified as the anion constituting the salt treating agent, for example, hexafluorophosphate, tetrafluoroborate, tetraphenyl borate and the like are exemplified. It is not limited to these.

  These treating agents may be used alone or in combination of two or more. These combinations may be used in combination with the treatment agent added at the start of the treatment, or may be used in combination with the treatment agent added in the middle of the treatment. The chemical treatment can also be performed multiple 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 the adsorbed water and the interlayer water and use them as the component (B).
The heat treatment method of the adsorbed water and the interlayer water of the ion exchange layered silicate is not particularly limited, but it is necessary to select the conditions so that the interlayer water does not remain and the structural destruction does not occur. The heating time is 0.5 hours or more, preferably 1 hour or more. At that time, the water content of the component (B) after removal is preferably 3% by weight or less, when the water content after dehydration for 2 hours under a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight. Is preferably 1% by weight or less.

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

  The ion exchangeable layered silicate can be treated with the component (C) described later and is preferred, prior to catalyst formation or use as a catalyst. Although there is no restriction | limiting in the usage-amount of the component (C) with respect to ion exchange layered silicate 1g, 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 or time, and 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 preferred to wash after treatment. The solvent used is a hydrocarbon solvent similar to the solvent used in the prepolymerization or slurry polymerization described later.

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

The granulation method used here includes, for example, a stirring granulation method and a spray granulation method, but commercially available products can also be used.
In granulation, organic substances, inorganic solvents, inorganic salts, and various binders may be used.
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 the crushing in the polymerization step and the formation of fine powder. In the case of such particle strength, particularly when performing prepolymerization, the effect of improving the particle properties is exhibited effectively.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. The organoaluminum compound used as the component (C) is suitably a compound represented by the general formula: (AlR ¹¹ _q Z _3-q ) _p .
It goes without saying that the compounds represented by this formula can be used alone, in combination of two or more, or in combination. In this formula, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q is an integer of 1 to 3 and p is an integer of 1 to 2; As R ¹¹ , an alkyl group is preferable, and in the case of halogen, Z is chlorine, in the case of an alkoxy group, an alkoxy group having 1 to 8 carbon atoms, and in the case of an amino group, C 1 to 1 carbon An amino group of 8 is preferred.

Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, trinolmalpropylaluminum, trinolbutylaluminum, triisobutylaluminum, trinolhexyl aluminum, trinoloctylaluminum, trinolmaledecyl aluminum, diethylaluminum chloride, diethylaluminum Sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like can be mentioned. Among these, preferred are trialkylaluminums and alkylaluminum hydrides of p = 1 and q = 3. More preferably, R ¹¹ is trialkylaluminum having 1 to 8 carbon atoms.

(4) Formation of catalyst / prepolymerization The catalyst can be formed by contacting the above components in the (pre) polymerization tank simultaneously or continuously, or at one time or several times.
The contacting of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably performed between -20 ° C and 150 ° C. The contact sequence may be any desired combination, but it is as follows if particularly preferable ones are shown for each component.
When using the component (C), before contacting the component (A) with the component (B), the component (A) and / or the component (B) or both the component (A) and the component (B) Contacting component (C), contacting component (C) simultaneously with contacting component (A) with component (B), or after contacting component (A) with component (B) It is possible to contact (C). Preferably, before contacting the component (A) with the component (B), the catalyst component (C) is contacted with either or both of the catalyst component (A) and the catalyst component (B).
Moreover, after contacting each component, it is possible to wash | clean with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of catalyst components (A), (B) and (C) used is optional. For example, the amount of catalyst component (A) used relative to catalyst component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, per 1 g of catalyst component (B). Further, the amount of the catalyst component (C) to the catalyst component (A) is preferably 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ in molar ratio of transition metal. .

Although the ratio of component [A-1] and component [A-2] is arbitrary in the range with which the characteristic of a propylene polymer is satisfied, it is [to the total amount of each component [A-1] and [A-2]. The molar ratio of the transition metal of A-1] is preferably 0.30 or more and 0.99 or less.
By changing this ratio, it is possible to adjust the balance between the melt physical properties and the catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight copolymer is produced by partially copolymerizing the macromer. Therefore, by changing the proportion of the component [A-1], the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution to the high molecular weight side, very high molecular weight components, branching (Distribution) can be controlled, whereby it is possible to control melt physical properties such as strain hardening degree, melt tension and melt spreadability. In order to produce a higher strain hardening propylene-based polymer, it is usually 0.30 or more, preferably 0.40 or more, and more preferably 0.5 or more. The upper limit is 0.99 or less, preferably 0.95 or less, and more preferably 0.90 or less in order to obtain a propylene-based polymer efficiently with high catalytic activity.
Moreover, it is possible to adjust the balance of an average molecular weight and catalyst activity with respect to the amount of hydrogen by using component [A-1] in the said range.

  The catalyst is subjected to a prepolymerization process which comprises contacting this with an olefin and polymerizing a small amount. By performing the prepolymerization treatment, the formation of a gel can be prevented when the main polymerization is performed. The reason is considered to be that the long chain branching can be uniformly distributed among polymer particles when the main polymerization is performed, and it is possible to improve the melt physical properties by that.

  The olefins used in the prepolymerization are not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinyl cycloalkane, Styrene etc. can be illustrated. The olefin can be fed by any method such as a feed method or a combination thereof in which the olefin is maintained at a constant rate or constant pressure in the reaction vessel, or 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, based on the amount of the prepolymer (B). Moreover, component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after completion of the prepolymerization.

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

(5) Use of catalyst / Regarding propylene polymerization As the polymerization mode, any mode can be adopted as long as the catalyst for olefin polymerization containing the component (A), the component (B) and the component (C) efficiently contacts the monomer. sell.
Specifically, a slurry method using an inert solvent, a so-called bulk method using propylene as a solvent substantially without using an inert solvent, a solution polymerization method, or each monomer in gaseous form substantially without using a liquid solvent It is possible to adopt a gas phase method for keeping it. In addition, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, multistage polymerization of two or more stages is also possible.

In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as a polymerization solvent.
Moreover, polymerization temperature is 0 degreeC or more and 150 degrees C or less. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C. or more, more preferably 50 ° C. or more. The upper limit is preferably 80 ° C. or less, more preferably 75 ° C. or less.
Furthermore, in the case of using gas phase polymerization, the temperature is preferably 40 ° C. or more, more preferably 50 ° C. or more. The upper limit is preferably 100 ° C. or less, more preferably 90 ° C. or less.

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, in the case of using bulk polymerization, it is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, in the case of using gas phase polymerization, it is preferably 1.5 MPa or more, more preferably 1.7 MPa or more. The upper limit is preferably 2.5 MPa or less, more preferably 2.3 MPa or less.

Furthermore, as a molecular weight modifier, and for the effect improvement effect, supplemental use of hydrogen in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene it can.
Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the produced polymer, the molecular weight distribution, the deviation of molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, (Distribution) can be controlled, whereby it is possible to control melt physical properties such as strain hardening degree, melt tension and melt spreadability.
Therefore, hydrogen is preferably used at a molar ratio of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, and more preferably 1.0 × 10 ⁻⁴ or more. Is good. The upper limit is preferably 1.0 × 10 ⁻² or less, preferably 0.9 × 10 ⁻² or less, and more preferably 0.8 × 10 ⁻² or less.

  In addition to the propylene monomer, copolymerization may be performed using, as the comonomer, an α-olefin comonomer having 2 to 20 carbon atoms excluding propylene, such as ethylene and / or 1-butene, depending on the use.

Therefore, in order to obtain a propylene polymer (X) having a good balance of catalytic activity and melt property,
Further, in order to obtain a polymer having a good balance of heat seal and strain hardening degree (λmax), ethylene and / or 1-butene is preferably used in an amount of 0.5 mol% or more based on propylene, preferably 1 It is at least 0.1 mol%, more preferably at least 1.5 mol%. In order to have a certain degree of strain hardening, it is necessary to use ethylene and / or 1-butene at 15 mol% or less to propylene, preferably 10.0 mol% or less, more preferably Is 7.0 mol% or less.
However, in order to obtain a polymer having high crystallinity and a high degree of strain hardening (λmax) as described above, polymerization using no comonomer is preferable.

[Propylene-ethylene block copolymer (Y)]
The propylene-ethylene block copolymer (Y) to be blended together with the above-mentioned propylene-based polymer (X) having a branched structure is produced separately even if it is a mixture by the sequential polymerization method (polymerization and blending method) described later The propylene-based polymer component (A) and the propylene-ethylene random copolymer component (B) are mixed in a mixing apparatus, for example, a ribbon blender, a Henschel mixer (trade name), a Banbury mixer, a drum tumbler, a single shaft or two. The mixture may be a mixture obtained by a melt-kneading method (melt-blending method) using a screw extruder, a co-kneader, etc. However, it is preferable to economically manufacture by sequential polymerization.
The term “sequential polymerization” means two or more continuous multistage polymerizations. The mixture by the sequential polymerization method as referred to herein is a commonly called block copolymer obtained by sequentially polymerizing the component (A) and the component (B), and the component (A) and the component (B) are not necessarily required. May not be completely copolymerized in block form. Although this block copolymer (Y) is obtained by continuous polymerization, substantially, a combination of a propylene-based polymer component (A) and a propylene-ethylene random copolymer component (B) It is. However, since the block copolymer (Y) is obtained by sequential polymerization, after each of these (co) polymers is produced in an independent reactor, each of the obtained (co) polymers is machined. It has a micro phase separation structure or a bicontinuous structure, as compared with a composition mixed in a simple manner.
The above-mentioned crystallinity means that lamella can be formed due to high stereoregularity and relatively low comonomer content in the copolymer. That is, the propylene-based polymer component (A) is crystalline, exerts heat resistance, and suppresses stickiness and bleed out.
On the other hand, the low crystallinity or non-crystallinity is lower in crystallinity than the crystallinity of the propylene-based polymer component (A) or is crystallinity in various methods for evaluating crystallinity such as TREF described later Means that it can not be observed.

  The preferred preparation of the propylene-ethylene block copolymer (Y) used in the present invention comprises, in the first step, the propylene-based polymer component (A) and in the second step the propylene-ethylene random copolymer component (B). It is to sequentially polymerize. Hereinafter, the propylene-ethylene block copolymer (Y) by the sequential polymerization method will be specifically described.

(1) Propylene-based polymer component (A) obtained in the first step [hereinafter, also referred to as polymer component (A). ]
In the present invention, the polymer component (A) to be polymerized in the first step mainly refers to a crystalline propylene homopolymer, but propylene and a small amount of 2 to 20 carbon atoms unless it deviates from the spirit of the invention. And copolymers with other .alpha.-olefins. Here, ethylene, 1-butene, 1-hexene, 1-octene etc. can be illustrated as another alpha-olefin.
The polymer component (A) is preferably a propylene homopolymer component because it is a component that contributes to rigidity and heat resistance in a propylene-ethylene block copolymer.

  0 to 15 weight% is preferable, as for the comonomer content of a polymer component (A), 0 to 5 weight% is more preferable, and 0 to 2 weight% is especially preferable. When the content of the comonomer is increased, the impact resistance is improved, and the polymerization activity at the time of production is significantly increased and the production cost is reduced. However, when the content of the comonomer is 15% by weight or less, the decrease in heat resistance is suppressed. It becomes easy to control stickiness and bleed out. In addition, the particle properties are not deteriorated in the middle of the first step and can not be polymerized.

  Furthermore, as for a polymer component (A), it is preferable that melting peak temperature Tm (A) by the differential scanning calorimeter (DSC) which is a scale of crystallinity is in the range of 150-165 degreeC. Tm (A) is measured as a melting peak temperature obtained by a differential scanning calorimeter (DSC) in a conventional manner with respect to the polymer component (A) sampled in a small amount after completion of the first step. Heat resistance improves that Tm (A) is 150 ° C or more, and when processing is performed at high temperature such as retort treatment, the film does not soften or fusion between the films is not observed due to high temperature processing . Moreover, the problem of becoming easy to be taken by a roll at the time of film formation does not arise. Adjustment of melting peak temperature Tm (A) can be performed by the ethylene content in powder.

(2) Propylene-ethylene random copolymer component (B) obtained in the second step [hereinafter, also referred to as copolymer component (B). ]
The copolymer component (B) is a low crystalline or non-crystalline component and is a component that contributes to the flexibility and impact resistance of the present copolymer. This component is mainly polymerized as a propylene-ethylene random copolymer in the second and subsequent stages of the multistage polymerization method. Here, as long as the purpose of the present invention is not deviated, it may be copolymerized with a small amount of other α-olefins such as 1-butene, 1-hexene, 1-octene and the like. The copolymer component (B) is one having an ethylene content E (B) of usually 10 to 85% by weight, preferably 15 to 80% by weight, particularly preferably 20 to 75% by weight. The impact resistance of a block copolymer improves that E (B) is 85 weight% or less, and especially the impact resistance in low temperature improves. The impact resistance is also improved when E (B) is 10% by weight or more.

In the copolymer component (B), the proportion W (B) in the total amount of the copolymer (Y) is usually 10 to 50% by weight, preferably 10 to 40% by weight. When W (B) is 50% by weight or less, aggregation of polymer particles is reduced, heat resistance of the copolymer (Y) is improved, stickiness and bleed out are easily suppressed, and W (B) When it is 10% by weight or more, the amount of the copolymer component (B) contributing to the flexibility and the impact resistance is sufficient, and the flexibility and the impact resistance are improved.
MFR of a copolymer component (B) is calculated | required by converting the mass mean molecular weight MwEPR of the copolymer component (B) calculated | required by the cross fractionator from the correlation type | formula of MFR and a mass mean molecular weight. For simplicity, it can be easily calculated from W (B), MFR (A), and MFR of the entire copolymer (Y), using the fact that the natural logarithm of MFR is proportional to the mass average molecular weight. There is essentially no difference in the calculation method. The adjustment of the MFR of the copolymer component (B) can be carried out by adjusting the amount of hydrogen to be supplied, or the polymerization temperature.

  The ratio W (B) of the copolymer component (B) to the total amount of the copolymer (Y) can be obtained by dividing the polymerization amount in the second step by the polymerization amount of the entire copolymer (Y). Specifically, the amount of polymerization in the second step can be calculated from the amount of consumed monomers, heat of reaction, increased mass of the reactor itself, etc. Therefore, it can be divided by the amount of polymerization of the whole copolymer (Y). In the case of continuous polymerization in which reactors are connected in series, it can be calculated from the production amount per hour in the first and second steps. Also, as a simple method, the polymer component (A) obtained in the first step and the copolymer component (B) obtained in the second step are fractionated by solvent fractionation (for example, cold xylene soluble fraction fractionation method) Can also be calculated from their respective masses. Furthermore, the mass ratio of the polymer component (A) obtained in the first step to the copolymer component (B) obtained in the second step can also be determined by instrumental analysis such as TREF or CFCIR.

  The method for evaluating the crystallinity distribution of the copolymer component (B) by temperature rising elution fractionation (TREF) is well known to those skilled in the art, and for example, measurement methods detailed in the following documents etc. It is shown. 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. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995).

  The copolymer (Y) used in the present invention has a large difference in the crystallinity between the polymer component (A) and the copolymer component (B), and each of them is produced by using a metallocene catalyst. Because the distribution of crystallinity is narrow, there are very few intermediate components between the two, and it is possible to accurately separate both by TREF. W (B) is controlled by changing the ratio of the production amount of the first step of producing the polymer component (A) and the production amount of the second step of producing the copolymer component (B) it can. For example, in order to increase W (A) and reduce W (B), it is sufficient to reduce the production amount of the second step while maintaining the production amount of the first step, which shortens the residence time of the second step The temperature can be easily controlled by decreasing the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.

The ethylene content E (AB) of the entire copolymer (Y) can be determined from the ¹³ C-NMR spectrum by the proton complete decoupling method. The assignment of spectra can be referred to, for example, Macromolecules 17 1950 (1984). In addition, several 13 samples of standard samples of copolymers different in ethylene content are prepared in advance, their 13 C-NMR spectrum and infrared absorption spectrum are measured, and a calibration curve for obtaining ethylene content is prepared from this, and converted using this You may Alternatively, a calibration curve in CFC-IR (combination of a cross fractionator and Fourier transform infrared absorption spectrum analysis) may be prepared and used.

The ethylene content E (B) in the copolymer component (B) in the second step is expressed by the following formula 2 from the ethylene content E (AB) of the entire copolymer and the above-mentioned E (A) and W (B) It can be calculated.
(Formula 2) E (B) = (E (AB) -E (A) * (1-E (B))) / W (B)

  The MFR of the copolymer (Y) is preferably 1 to 50 dg / min. More preferably, it is 3 to 40 g / 10 minutes, further preferably 5 to 30 g / 10 minutes. When the MFR is in the range of 1 to 50 g / 10 min, the compatibility with the propylene-based polymer (X) is good, the processability of extrusion lamination processing is good, and the extrusion laminate is excellent in spreadability and high speed. Is possible.

  The mass average molecular weight of the copolymer component (B) in the copolymer (Y) is preferably 10,000 to 5,000,000. A mass average molecular weight of 10,000 or more is preferable because the impact resistance of a product obtained by forming the copolymer (Y) is improved. In addition, the mass average molecular weight of 5,000,000 or less is preferable because the appearance of the product is improved. The preferable lower limit of this range is 50,000, and the more preferable lower limit is 100,000. The preferable upper limit of this range is 3,000,000, and the more preferable upper limit is 1,000,000. The measurement is by CFC-IR.

[Method for producing propylene-ethylene block copolymer (Y)]
The preferred propylene-ethylene block copolymer (Y) used in the present invention comprises a propylene-based polymer component (A) in the first step, It is obtained by sequentially polymerizing propylene-ethylene random copolymer component (B) in the process.

(Vii) The melting peak temperature Tm (A) of the propylene-based polymer component (A) is 150 to 165 ° C.
(Viii) The ratio [W (B)] of the propylene-ethylene random copolymer component (B) to the total amount of the propylene-ethylene block copolymer (Y) is 10 to 50% by weight.
(Ix) The ethylene content [E (B)] of the propylene-ethylene random copolymer component (B) is 10 to 85% by weight.

(1) Polymerization Catalyst The propylene-ethylene block copolymer (Y) is not limited in the method for producing it, and may be produced by using a Ziegler-Natta catalyst, or may be produced by using a metallocene catalyst.

  Ziegler-Natta catalysts are described, for example, in "Polypropylene Handbook" by Edward P. Moore Jr. A catalyst system as outlined in ed., Translation by 保, 暢, 佐, 2, Section 2.3.1 (pages 20-57) of the Industrial Survey Committee (1998), eg, titanium trichloride and halogen A titanium trichloride-based catalyst consisting of an organoaluminum, a solid catalyst component essentially containing magnesium chloride, titanium halide, an electron donating compound, a magnesium-supported catalyst consisting of an organoaluminum and an organosilicon compound, and a solid catalyst component It refers to a catalyst in which an organoaluminum compound component is combined with an organosilicon-treated solid catalyst component formed by bringing an organoaluminum and an organosilicon compound into contact with each other.

  On the other hand, single-site catalysts such as metallocene catalysts have higher catalytic activity, a narrower molecular weight distribution of the produced polymer, and a uniform composition distribution in copolymers, as compared with Ziegler-based catalysts. It is a better catalyst than Ziegler-based catalysts for producing polymers. The details will be described later.

(2) Polymerization Method The propylene-ethylene block copolymer (Y) used in the present invention is produced in the first step as a crystalline propylene-based polymer component (A) as the first step, and obtained in the first step as the second step. In the presence of the polymerization reaction mixture, a low crystalline or non-crystalline propylene-ethylene random copolymer component (B) is continuously produced.

  As a polymerization method, solution polymerization, slurry polymerization, gas phase polymerization and bulk polymerization are possible. The polymerization in the first step is the polymerization of a crystalline propylene-based polymer component (A), and is usually a slurry polymerization method or a gas phase polymerization method in which each monomer is kept in a gaseous state substantially without using a liquid solvent. Is adopted. Moreover, as for the mode of polymerization in the first step, bulk polymerization using propylene as a solvent substantially without using an inert solvent can also be adopted if the catalyst component and each monomer are in efficient contact. There is no particular limitation on the polymerization method, but bulk polymerization and gas phase polymerization are preferable. The preferred gas phase polymerization method is a method of performing polymerization in gaseous monomer without using a medium, for example, a method in which the produced polymer particles are flowed by a monomer flow to form a fluidized bed, or a produced polymer particles are stirred by a stirrer It is a system which stirs in a reaction tank. The bulk polymerization and the gas phase polymerization are preferable because a high boiling point solvent does not exist in the system, so that the removal step of the solvent is not necessary.

  The polymerization step of the second step polymerizes the propylene-ethylene random copolymer component (B) having a high ethylene content in the presence of the catalyst-containing propylene-based polymer component (A) obtained in the polymerization of the first step It is a process. There is no particular limitation on the polymerization method, but preferred is gas phase polymerization. Gas phase polymerization is preferred because the ethylene content of the propylene-ethylene random copolymer component (B) is high, so in polymerization processes other than the gas phase process, the liquid (solvent or liquid propylene) present in the polymerization system is propylene- This is because the ethylene random copolymer component (B) is easily dissolved, and the polymer particles tend to be sticky. This is further promoted when the content W (B) of the propylene-ethylene random copolymer component (B) in the present copolymer is high. Therefore, first, the propylene-based polymer component (A) is polymerized by the bulk method or the gas phase method using the continuous method, and then the propylene-ethylene random copolymer component (B) is polymerized by the gas phase method Is particularly preferred.

(3) Polymerization conditions (3-1) Polymerization temperature The polymerization temperature is usually 0 to 150 ° C. The lower limit thereof is preferably 50 ° C., more preferably 60 ° C., and the upper limit thereof is preferably 90 ° C., more preferably 80 ° C. If the temperature is lower than the lower limit, there is no problem that the polymerization activity is lowered or the heat removal efficiency of reaction heat is deteriorated, and if the temperature is lower than the upper limit, there is no problem that the produced polymer becomes sticky. The upper limit temperature is also related to the melting point Tm (A) of the propylene-based polymer component (A), and in particular, the temperature is not more than Tm (A)-40 ° C, in particular not more than Tm (A)-50 ° C preferable.

(3-2) Polymerization pressure polymerization pressure is typically greater than 0 kg / cm ² G, or less 2,000kg / cm ² G. The lower limit of the pressure is preferably 5 kg / cm ² G, more preferably 10 kg / cm ² G, particularly preferably 15 kg / cm ² G. If the content is at least the lower limit, problems such as reduction in polymerization activity or decrease in molecular weight do not occur. The preferred upper limit is 60 kg / cm ² G. The gas phase polymerization is carried out under temperature and pressure conditions at which the gas phase can be maintained by introducing propylene or a mixed monomer of propylene and ethylene. Bulk polymerization is preferably performed under temperature and pressure conditions that can keep propylene or a mixed monomer of propylene and ethylene in a liquid state. The polymerization time is usually 5 minutes to 10 hours, preferably 15 minutes to 7 hours, more preferably 30 minutes to 5 hours.

(3-3) Ratio of Monomers In the case of continuous copolymerization, the quantitative ratio of each monomer in the reaction system does not have to be constant over time, and each monomer can be supplied at a constant mixing ratio, and supplied. It is also possible to change the mixing ratio of the monomers over time. In addition, hydrogen can be additionally used as a molecular weight regulator of the produced polymer.

  In the present invention, it is desirable that the copolymerization be carried out at a propylene / ethylene molar ratio (hereinafter also referred to as a monomer molar ratio (A)) in the reaction system in the first step polymerization of 100/0 to 80/20. In 80/20 of a lower limit molar ratio, it is preferable in order that rigidity will improve that propylene is 80 or more. These values are measured by gas chromatograph.

  It is desirable that the copolymerization be carried out at a propylene / ethylene molar ratio (hereinafter also referred to as a monomer molar ratio (B)) in the reaction system in the second step polymerization of 10/90 to 90/10. It is preferable that propylene is 10 or more at a lower limit molar ratio of 10/90 because impact resistance is improved. On the other hand, the impact resistance is similarly improved even if propylene is 90 or less at the upper limit of the molar ratio of 90/10. These values are measured by gas chromatograph. An inert gas such as nitrogen, propane or isobutane can be allowed to coexist in the polymerization system, but if it is present in a large amount, the partial pressure of the monomer is lowered to cause low activity, which is not preferable. The proportion of these inert gases may be 20 mol% or less, preferably 10 mol% or less.

(3-4) Multistage polymerization It is preferable to carry out the polymerization reaction by multistage polymerization. As an example of multistage polymerization, there is a mode in which the catalyst is continuously supplied to the uppermost stream reactor of a plurality of reactors connected in series, and the polymer is continuously extracted and transferred to the subsequent polymerization tank. As another example, the catalyst is continuously supplied to one polymerization tank to carry out the first-stage polymerization, and then the monomer is purged, without deactivating the catalyst present in the polymerization tank. A method of carrying out the second stage polymerization can also be exemplified. In any case, since the monomer brought in from the previous step and the previous polymerization, hydrogen and the like less affect the next step, the amount of purge of monomers etc. is increased before transferring the step, or with an inert gas such as nitrogen. It is also possible to dilute or replace, but it is preferred to do so.
The polymerization reaction in the second step in the present invention refers to the polymerization reaction carried out after the polymerization reaction under at least one condition, for example, the copolymer component carried out after carrying out the polymerization of the propylene-based polymer component (A) in multiple steps. The polymerization of (B) is also included. Each of the first and second steps can be divided into several steps. Specifically, there are a method in which a plurality of reactors are connected in series and each step is divided into several steps, and a method in which each step is performed in a plurality of batches using one reactor.

(3-5) Killer Compound The killer compound is a compound which reduces the activity of the polymerization catalyst (in particular, the activity of the second step) and deactivates it. Killer compounds selectively capture and deactivate short pass particles smaller than normal catalyst particles. This suppresses the formation of particles in which the content [W (B)] of the copolymer component (B) is excessive. As a killer compound, usually, a compound having polarity such as oxygen, ethanol, acetone or the like is used. When using a metallocene catalyst, it is a compound which does not have active hydrogen that reacts with or interacts with an aluminum compound (scavenger), while having a polar group that interacts with the single site active site of the metallocene catalyst. Good. Such compounds include alkyl halides, ethers and vinyl ethers. In multistage continuous polymerization, the killer compound may be supplied to any polymerization reactor. Preferably, it is supplied to the reactor that performs the second step. When the second step is carried out in a plurality of reactors, it is preferable to supply the top stream reactor. If particles having an excess of W (B) are present, the melting of the copolymer and the dispersion of the copolymer component (B) in molding become insufficient at the time of molding, causing appearance defects due to the generation of bright spots, gels and the like. At the same time, it causes a decrease in the impact resistance of the copolymer. In addition, since many killer compounds act on the surface of polymer particles in the reactor, only the active points on the surface are selectively deactivated, the amount of surface stickiness components is reduced, and the particles become sticky. Adhesion to the wall is also suppressed. Furthermore, addition of a killer compound is also used as a means of controlling the polymerization activity of the second step. This makes it possible to control the amount (W (B)) of the component (B) relative to the total amount of the copolymer.

(3-6) Particle size of polymer particles after completion of the first step In the present invention, although the second step is carried out after the completion of the first step, the copolymer component (B) having a high ethylene content and being easily sticky is The point is how to stably produce in the process. For stable production, it is necessary to prevent the adhesion of easily tacky polymer particles. For that purpose, it is important to increase the particle size of the polymer particles after the completion of the first step, that is, the particle size of the polymer particles before the start of the second step. When the particle size of the polymer particle is large, the effect of the killer compound is easily exhibited as described above, and the specific surface area of the polymer particle is small, and the contact area of the polymer particle per unit mass is small, The speed at which the coalescing component (B) bleeds out to the surface (moves to the surface of the polymer particles) can be reduced. Therefore, there is a preferred range for the average particle size of the polymer particles after completion of the first step, and the lower limit is usually 800 μm, preferably 1000 μm, more preferably 1100 μm.

(3-7) Amount of fine powder of polymer particles after completion of the first step Not only the above conditions, but also fine particles of polymer particles affect the operation stability of the reactor. If this amount is large, adhesion to the reactor wall, clogging in the transfer piping, scattering to the gas piping, clogging of the filter, and the like may occur to adversely affect the operation stability. The amount of fine powder is represented by the amount of fine powder having a particle size of 212 μm or less in the particle size distribution measurement, and the polymer particles can be sieved with a sieve with a pore size of 212 μm and quantified at a rate passing through it. The amount of fine powder is preferably 2.0% by weight or less, more preferably 1.0% by weight or less, particularly preferably 0.5% by weight or less, and in particular 0.1% by weight or less.

3. Polymerization Catalyst Suitable for Production of Propylene-Ethylene Block Copolymer (Y) (1) Metallocene-Based Catalyst To produce the propylene-ethylene block copolymer (Y) in the present invention, as described above, a metallocene-based catalyst is used. It can be used. It is widely known to those skilled in the art that a broad molecular weight and crystallinity distribution in a propylene-ethylene block copolymer degrades stickiness and bleed-out, but it is also for the copolymer to suppress stickiness and bleed-out. Alternatively, they can be prepared by polymerization using a metallocene catalyst capable of narrowing molecular weight and crystallinity distribution.

  The metallocene catalyst generally activates a metallocene complex comprising a transition metal compound of Groups 4 to 6 of the periodic table (short cycle type) having a conjugated five-membered ring ligand (I) and (II) It is composed of a cocatalyst, and optionally used (III) organoaluminum compound. Depending on the properties of the olefin polymerization process, since the formation of particles is essential, the (IV) carrier may be a component.

(I) Metallocene Complex Representative examples of the metallocene complex used in the present invention include metallocene bridged complexes of transition metal compounds of Groups 4 to 6 of the periodic table having conjugated 5-membered ring ligands, Among them, those represented by the following general formula, among them, those of azulene type are preferable.

(Wherein, M is Ti, Zr or Hf. X and Y are auxiliary ligands, which react with a cocatalyst of component (II) to form an active metallocene having olefin polymerization ability) Z and Z 'are an optionally substituted indenyl group, fluorenyl group or azulenyl group Q is a group which bridges Z and Z' Z and Z 'are further Each ring may have a substituent.)

  As Z and Z ', an indenyl group or an azulenyl group, particularly an azulenyl group is preferable. Q represents a bonding group which bridges at an arbitrary position between ligands such as two conjugated five-membered rings, and is specifically preferably an alkylene group, a silylene group or a germylene group. M is a metal atom of a transition metal selected from Groups 4 to 6 of the periodic table, preferably titanium, zirconium, hafnium or the like. Particularly preferred is zirconium or hafnium. X and Y are auxiliary ligands, which react with the cocatalyst of component (II) to form an active metallocene having olefin polymerization ability. Therefore, X and Y are not limited in kind of ligand as long as the object is achieved, and each may be a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon group which may have a hetero atom. Etc. can be illustrated. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable. The following can be illustrated as specific compounds of the metallocene complex.

  In a metallocene complex having a structure in which a substituent has two cyclopentadienyl ligands of which the ring is composed and these are bridged, as an azulene group, dimethylsilylene bis {1- (2- (2-) Methyl-4-isopropyl-4H-azulenyl)} zirconium dichloride, dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azulenyl)} zirconium dichloride, dimethylsilylene bis [1- {2-methyl-4- 4- (4-Chlorophenyl) -4H-azulenyl}] zirconium dichloride, dimethylsilylene bis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride, dimethylsilylene bis [1- {2 -Methyl-4- (3-chlorophenyl) -4H-azulenyl}] zirconium Chloride, dimethylsilylene bis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride, dimethylsilylene bis {1- (2-methyl-4,6-diisopropyl-4H) -Azulenyl)} zirconium dichloride, diphenylsilylene bis {1- (2-methyl-4-phenyl-4H-azulenyl)} zirconium dichloride, methylphenylsilylene bis {1- (2-methyl-4-phenyl-4H-azulenyl) } Zirconium dichloride, methylphenylsilylene bis [1- {2-methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, dimethylsilylene bis {1- (2-ethyl-4-phenyl-4H-azulenyl) )} Zirconium dichloride, dimethyl silile Bis [1- {2-ethyl-4- (1-anthracenyl) -4H-azulenyl]] zirconium dichloride, dimethylsilylene bis [1- {2-ethyl-4- (2-anthracenyl) -4H-azulenyl}] zirconium Dichloride, dimethylsilylene bis [1- {2-ethyl-4- (9-phenanthryl) -4H-azulenyl}] zirconium dichloride, dimethylmethylene bis [1- {2-methyl-4- (4-biphenylyl) -4H- Azulenyl} zirconium dichloride, dimethylgermylene bis [1- {2-methyl-4- (4-biphenylyl) -4H-azulenyl}] zirconium dichloride, dimethylsilylene bis {1- (2-ethyl-4- (3 ,, 5-dimethyl-4-trimethylsilylphenyl-4H-azulenyl)} zirconium Mudichloride, etc. may be mentioned.

  Examples of azulene-based compounds which are different from other conjugated multi-membered ring ligands include dimethylsilylene [1- {2-methyl-4- (4-biphenylyl) -4H-azulenyl}] [1- {2- Methyl-4- (4-biphenylyl) indenyl} zirconium dichloride, dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azulenyl)} {1- (2-methyl-4,5-benzoindenyl) } Zirconium dichloride and the like can be mentioned.

  As a metallocene complex having a structure in which two indenyl ligands are linked and they are bridged, dimethylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, dimethyl silylene bis {1- (2-Methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, diphenylsilylene bis {1- (2-) Methyl-4-phenylindenyl)} zirconium dichloride, methylphenylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {1- (2-ethyl-4-phenylindenyl) ) Zirconium dichloride, dimethylgermylene bis {1- 2-ethyl-4-phenylindenyl)} zirconium dichloride, methylaluminum bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, phenyl phosphino bis {1- (2-ethyl-4-phenyl) Indenyl)} zirconium dichloride, phenylamino bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride and the like.

  Examples of metallocene complexes having a structure in which one substituted fluorenyl ligand and one substituted cyclopentadienyl group are bridged with each other include isopropylidene (cyclopentadienyl-9-fluorenyl) titanium dichloride, isopropyl Phenylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2, 7-dimethyl-9-fluorenyl) titanium dichloride, Isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichlori , Isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride , Isopropylidene (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl 9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl 9-fluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl 9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl 2, 7-dimethyl-9-fluorenyl) titanium dichloride Diphenylmethylene (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl 2, 7-di-tert-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl 2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl 2,7- Di-t-butyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl 9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl 2,7-dimethyl) -9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclo) Pentadienyl 9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9) -Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl 9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl 2, 7-dime) -9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl 9-fluorenyl) titanium dichloride, diethyl Silanediyl (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediyl bis ( Tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl 9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl 2, 7-dime) 9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl 9-fluorenyl) hafnium dichloride, diethyl Silanediyl (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclo) Pentadienyl 9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl 2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylsilane diyl ( Cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl 9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl 2,7-dimethyl-) 9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl 2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl 9-fluorenyl) hafnium dichloride, diphenylsilanediyl (Cyclopentadienyl 2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl 2, 7-di-tert-butyl-9-fluorenyl) Dimethyl body hafnium dichloride dichloro body and the periodic table group 4 transition metal compounds, such as, diethyl body, dihydro derivative, diphenyl body, and the like can be exemplified dibenzyl body.

  Compounds in which the silylene group of the compounds of these specific examples is replaced by a germylene group and zirconium is replaced by hafnium or vice versa are also exemplified as preferable ones. Hafnium compounds are preferred if the molecular weight of the desired copolymer is high. The component (I) is preferably a coordination having a silylene group having a hydrocarbon substituent, a substituted cyclopentadienyl group bridged with a germylene group or an alkylene group, a substituted indenyl group, a substituted fluorenyl group, and a substituted azulenyl group. Preferred is a transition metal compound consisting of a molecule, in particular those which are bridged by a silylene group having a hydrocarbon substituent, or a germylene group, or a ligand having a substituted indenyl group or a substituted azulenyl group, particularly at the 2-position or Those having a substituent at the 4-position or 2-position and 4-position are preferred.

(II) Promoter (Activator component)
The co-catalyst is a component that activates the metallocene complex, and is a compound that can be reacted with an auxiliary ligand of the metallocene complex to convert the complex into an active species having an olefin polymerization ability. -1) to (II-4).
(II-1) Aluminum oxy compound (II-2) An ionic compound capable of converting component (I) to a cation by reacting with component (I) or Lewis acid (II-3) solid acid (II-) 4) Ion exchange layered silicate

  It is well known that the aluminum oxy compound (II-1) can activate a metallocene complex, and specific examples of such a compound include compounds represented by the following general formulas.

In each of the above general formulas, R ¹ represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P is an integer of 0 to 40, preferably 2 to 30. Among the general formulas, the compounds represented by the first and second formulas are compounds also called aluminoxanes, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxane can be used in combination of two or more species in each group and between each group. And, the above-mentioned aluminoxane can be prepared under various known conditions. The compound represented by the third of the general formula is 10: 1 to 10 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and the alkylboronic acid represented by the general formula R ² B (OH) ₂ It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula, R ¹ and R ² each represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

  The compound (II-2) is an ionic compound or a Lewis acid capable of reacting with the component (I) to convert the component (I) to a cation, and such ionic compounds include carbonium Examples thereof include a complex of a cation, a cation such as an ammonium cation, and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, and the like. Also, as the Lewis acid as described above, various organic boron compounds such as tris (pentafluorophenyl) boron and the like are exemplified. Alternatively, metal halides such as aluminum chloride and magnesium chloride are exemplified.

  In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with component (I) and can convert component (I) into a cation. Here, as a particulate carrier supporting component (II-1) and component (II-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include inorganic halides such as aluminum and lanthanum chloride, and further, porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene-divinylbenzene copolymer, and acrylic acid-based copolymer. As a solid acid of (II-3), alumina, silica-alumina, silica-magnesia etc. are mentioned.

  The ion exchangeable layered compound of (II-4) accounts for the majority of the clay mineral, and is preferably an ion exchangeable layered silicate. Ion exchange layered silicate (hereinafter sometimes simply referred to as “silicate”) has a crystal structure in which faces constituted by ionic bonds etc. are stacked in parallel with each other by bonding force, and contained Ion is an exchangeable silicate compound. Most silicates are naturally produced mainly as a main component of clay minerals, so they often contain contaminants (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. It may be. Various known silicates can be used. Specifically, mention may be made of the layered silicates described in "Clay Mineralogical Science" by Haruo Shiramizu, Asakura Shoten (1995), and the main component silicate is a silicate having a 2: 1 type structure. The smectite group is more preferable, and montmorillonite is particularly preferable. With regard to silicates, those obtained as natural products or industrial raw materials can be used as they are without particular treatment, but chemical treatment is preferred. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. These processes may be used in combination with each other. There is no particular limitation on these processing conditions, and known conditions can be used.

In addition, since these ion exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use after removing water, for example, by heat dehydration treatment under an inert gas flow. Although the ion exchangeability may be reduced depending on the degree of the chemical treatment, if the raw material before the chemical treatment is an ion exchange layered silicate, there is no particular problem.
As component (II) which is a cocatalyst, the ion exchangeable layered compound of II-4 is preferable because it is stable and excellent in performance and does not react violently with air or water.

(III) Organoaluminum Compound As the organoaluminum compound optionally used in the metallocene catalyst system, one containing no halogen is used, and specifically, a compound represented by the following general formula is used.
AlR _{3-i X} i
(Wherein R represents a C1 to C20 hydrocarbon group, X represents hydrogen, an alkoxy group, and i represents a number of 0 ≦ i ≦ 3), provided that when X is hydrogen, i is 0 ≦ i <3. Do.)

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trioctylaluminum, etc., or dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide, etc. Examples include alkoxy-containing alkylaluminums, and further, halide-containing alkylaluminums such as diethylaluminum halide.
Among these, in particular, trialkylaluminum, particularly triisobutylaluminum and trioctylaluminum are preferable.

(IV) Carrier As the carrier which is suitably used as needed in the metallocene catalyst system, various known inorganic or organic fine particulate solids can be mentioned. The average particle size of the carrier is usually 5 to 300 μm, preferably 30 to 300 μm, more preferably 40 to 250 μm, and particularly preferably 46 to 200 μm. The specific surface area of the carrier is usually 50~1,000m ² / g, preferably from 100 to 500 m ² / g, pore volume of the support is usually 0.1~2.5cm ³ / g, preferably 0 0.2 to 0.5 cm ³ / g. Examples of the inorganic solid include porous oxides, which are used after calcination at 100 to 1,000 ° C., preferably 150 to 700 ° C., if necessary.
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a mixture thereof, such as SiO ₂ -MgO, SiO ₂ -Al _{2 O 3, SiO 2 -TiO 2} , SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, etc. SiO ₂ -TiO 2 -MgO and the like. Among these, those having SiO ₂ or Al ₂ O ₃ as the main component are preferable.

Moreover, if it is a solid thing among said (II) co-catalysts, it is possible to use as a support | carrier co-catalyst, and preferable. As a specific example, (B-3) solid acid and (B-4) ion exchange layered silicate etc. are mentioned. In order to improve the particle properties of the block copolymer, it is preferable to carry out various known granulations.
Examples of the organic solid include (co) polymers formed mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc., or vinylcyclohexane, The solid of the polymer or copolymer produced | generated with styrene as a main component can be illustrated.

  In the illustration of each component (I) to (IV) of the above catalyst, each component of the catalyst does not constitute the essence of the present invention, so complicated and redundant listing is avoided and only a brief representative example is given. ing. In the present invention, it goes without saying that equivalent components other than those exemplified are also included, and there is no reason why these are excluded.

(2) Prepolymerization The catalyst of the present invention is preferably subjected to a prepolymerization treatment consisting of a small amount of polymerization in which an olefin is brought into contact in advance, in order to improve the particle property. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinyl cycloalkane, styrene and the like It is possible to use, in particular propylene is preferred. As an olefin supply method, any method may be employed such as a supply method or a combination thereof in which olefin is maintained at a constant velocity or constant pressure in the reaction vessel, or stepwise change. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The prepolymerization amount is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, based on 1 part by mass of the component (II). After the completion of the prepolymerization, it may be used as it is depending on the form of use of the catalyst, but if necessary it may be dried.

The prepolymerization temperature is not particularly limited, but is usually 0 ° C to 100 ° C, preferably 10 to 70 ° C, more preferably 20 to 60 ° C, and particularly preferably 30 to 50 ° C. Below this range, the reaction rate may decrease or the activation reaction may not proceed. If it exceeds, the prepolymerization polymer may be dissolved, or the prepolymerization speed may be too fast, resulting in deterioration of particle properties. There is a possibility that the adverse effect of deactivating the active site due to a side reaction may occur.
The prepolymerization can be carried out in a liquid such as an organic solvent, and it is preferable to do so. The concentration of the solid catalyst at the time of prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more the metallocene activation proceeds and the higher the activity of the catalyst.
Furthermore, it is also possible to coexist a polymer such as polyethylene, polypropylene or styrene or an inorganic oxide solid such as silica or titania upon or after the contact of the above-mentioned components.

[Proportion of Propylene-Based Polymer (X) and Propylene-Ethylene Block Copolymer (Y)]
The proportion of the propylene-based polymer (X) and the propylene-ethylene block copolymer (Y) in the polypropylene-based resin composition for extrusion lamination of the present invention is based on 100% by weight in total of (X) and (Y). And 3 to 50% by weight of a propylene-based polymer (X) and 97 to 50% by weight of a propylene-ethylene block copolymer (Y). By setting it in such a range, a resin composition for extrusion lamination having a small neck-in, excellent in laminateability, high spreadability, excellent in high-speed extrusion laminateability, and excellent in transparency and transparency of contents. It can be done.
The preferred composition range is 5 to 50% by weight of component (X), 95 to 50% by weight of component (Y), more preferably 10 to 40% by weight of component (X), 90 to 60% by weight %.

[Other ingredients]
In the polypropylene-based resin composition of the present invention, other resins other than the propylene-based polymer (X) and the propylene-ethylene block copolymer (Y) (for example, polyethylene-based polymers, various elastomers, etc.) Also, additives such as antiblocking agents, antioxidants, weathering stabilizers, antistatic agents, mold release agents, flame retardants, waxes, fungicides, antibacterial agents, fillers, foaming agents, etc. may be blended. .

[Extrusion lamination]
The polypropylene-based resin composition for extrusion lamination of the present invention is melt extrusion laminated (extrusion lamination) on the surface of a substrate and used to produce a laminate.
The extrusion laminating process is a molding process in which coating and adhesion are simultaneously performed by a method of continuously covering and pressing a molten resin film extruded from a T-die on the surface of a base material manufactured in advance. . Usually, it is laminated on one side surface of the substrate, but may be laminated on both sides if necessary.

Examples of the substrate include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, saponified ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, poly 4-methyl-1-pentene, polycarbonate resin, Films or sheets of thermoplastic resins such as polyamide resins such as polyamide 6, polyamide 66, polyamide 6.66, polyamide 12 and the like, paper, and metal foils such as aluminum and iron can also be mentioned.
The thermoplastic resin film or sheet may be uniaxially or biaxially stretched, and in particular, biaxially stretched polypropylene is preferable. Moreover, what laminated | stacked this with paper is also preferable.
The thickness of the substrate is usually about 5 to 100 μm.

The form of the substrate is not limited to a film or a sheet, and may be in the form of a woven fabric or a non-woven fabric. In addition, the substrate may have a single layer structure or a multilayer structure. It does not specifically limit as a preparation method of the base material of a multilayer structure, The co-pushing film method, the dry laminating method, the wet laminating method, the hot melt laminating method, the extrusion laminating method, the thermal laminating method etc. are mentioned.
Moreover, various film processing processes, such as anchor coating process, metal vapor deposition process, corona discharge treatment process, printing process, may be given to these base materials beforehand.

When extrusion laminating the polypropylene resin composition for extrusion lamination of the present invention on a substrate, the melt extrusion temperature of the resin composition is usually 180 to 320 ° C, preferably 200 to 310 ° C. Moldability is favorable in it being 320 degrees C or less.
Extrusion lamination is usually performed on one side of the substrate, but can be extrusion laminated on both sides as needed.

The thickness of the formed polypropylene resin composition layer is usually 1 to 250 μm, preferably 3 to 200 μm, and particularly preferably 5 to 150 μm.
The laminate obtained by extrusion lamination can be further subjected to various film processing such as metal vapor deposition, corona discharge treatment, printing and the like.

[Laminate]
The obtained laminate can be suitably used for packaging of various foods and beverages, medicines and medical products, cosmetics, clothes, stationery and other industrial materials, industrial materials and the like.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples.
The polypropylene resin composition and its components used in the examples and comparative examples, and the extrusion lamination formability and various physical properties of the laminate were measured and evaluated according to the following evaluation methods.

[Physical Properties of Each Propylene-Based Polymer]
(1) Melt flow rate MFR (unit: g / 10 minutes)
It measured based on the conditions M (230 degreeC, 2.16 kg load) based on the appendix of JISK6921-2: 1997. In addition, about polyethylene-type resin, the measurement temperature is 190 degreeC.
(2) Molecular weight distribution Mw / Mn
It was determined by GPC measurement according to the method described above.
(3) Ratio of Components with Molecular Weight (M) of 2 Million or More in Molecular Weight Distribution Curve by GPC Measured by GPC according to the method described above.
(4) Elution volume at a temperature of up to 40 ° C (temperature: elution elution fractionation (TREF) (unit: wt%)
Determined by TREF measurement according to the method described above.
(5) mm fraction (unit:%), ethylene content (unit: wt%)
The mm fraction was measured by the method described in paragraphs [0053] to [0065] of JP-A-2009-275207, using a superconducting nuclear magnetic resonance apparatus GSX-400 (400 MHz) manufactured by JEOL Ltd. and FT-NMR. .
Moreover, ethylene content was measured using the < ¹³ > C-NMR spectrum obtained by mm fraction measurement.

(6) Strain hardening degree λmax
The extensional viscosity measurement was performed under the following conditions.
Equipment: Ares manufactured by Rheometorics
-Jig: TA Instruments's Extentional Viscosity Fixture
・ Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
-Preparation of test piece: Press molding to form a sheet of 18 mm × 10 mm and a thickness of 0.7 mm.
Details of the calculation method of λmax are as described above.

(7) ME (memory effect)
Using a Takara melt indexer, apply a load to extrude the inside of an orifice diameter of 1.0 mm and a length of 8.0 mm at 190 ° C, and when the extrusion speed is 0.1 g / min, polymer extruded from the orifice Was quenched in ethanol, and the value of the strand diameter at that time was calculated as a value divided by the orifice diameter. This value is a value that correlates with Log (MFR), and when this value is large, it indicates that the swell is large and the product appearance when injection molding is improved.
(8) α / β
It was determined by GPC measurement according to the method described above.
(9) Melting point (unit: ° C)
Use a differential scanning calorimeter (DSC) and once raise the temperature to 200 ° C to erase the heat history, then drop the temperature to 40 ° C at a temperature decrease rate of 10 ° C / min and increase the temperature rise rate to 10 ° C / min again The temperature of the endothermic peak top at the time of measurement was taken as the melting point.

(10) Calculation of ethylene content E (A) in propylene-based polymer component (A) in the first step of propylene-ethylene block copolymer (Y) ¹³ C- described in JP-A 2003-73426 Based on the ethylene content of a standard sample calculated by ethylene content measurement by NMR, the peak height I [absorbance] and ethylene content E (A) [weight in the range of 700-760 cm ^{-1 in} infrared absorption spectrum] %] (Following formula [1]) was computed and it computed using this.
At the end of the first step, 5 g of the propylene-based polymer component (A) was extracted in advance, a 0.5 mm sheet of this was formed by press molding at 190 ° C., and the infrared absorption spectrum of the sheet was measured. D [mm] in the following formula [1] is a sheet thickness, and a numerical value accurately measured to 10 μm was used.
Formula [1] E (A) = 5 x I / D + 0.0613

(11) Rubber (ethylene-propylene copolymer (B) in the second step: EPR) content in propylene-ethylene block copolymer (Y) (= W (B)), ethylene content in EPR (E) (B)) and a method of measuring the mass average molecular weight (Mw _EPR ) of _EPR .
Cross fractionator (CFC T-100 manufactured by Dia Instruments Co., Ltd.), Fourier transform type infrared absorption spectrum analysis (FT-IR manufactured by Perkin Elmer 1760X), gel permeation chromatography (GPC) In the same manner, combinations (abbreviated as CFC-IR) were similarly measured and analyzed. W (B) was determined from the amount of the 40 ° C soluble matter of CFC-IR, and E (B) was determined from the ethylene content in the 40 ° C soluble matter of CFC-IR.

[Formability of extrusion lamination]
(1) Spreadability:
Cooling roll surface temperature 25 ° C., die width 300 mm, die lip using an extrusion laminating apparatus set so that the temperature of the resin extruded from a T-die attached to an extruder with a 35 mmφ is 290 ° C. The extrusion rate is adjusted so that the coating thickness is 15 μm when the drawing rate is 10 m / min at an opening degree of 0.7 mm, and extrusion is performed, and a biaxially stretched polypropylene film 400 mm wide and 20 μm thick (manufactured by Toyobo Co., Ltd.) Product name: Extrusion laminating was carried out while raising the take-up speed by 10 m / min on PYRENE FILM-OT P2161), and the maximum processing speed (unit: m / min) at which coating could be stably performed was defined as spreadability. The higher the spreadability, the better the extrusion laminating processability at high speed.
(2) Neck-in:
As described above, using an extrusion laminating apparatus, the extrusion laminating thickness is on a 20 μm thick biaxially stretched polypropylene film (manufactured by Toyobo Co., Ltd., trade name: Pyrene film-OT P2161) at a processing speed of 10 m / min. A laminate of 15 μm was prepared, and the difference between the die width and the width of the resin composition layer in the obtained laminate (unit: mm) was taken as the neck-in. The smaller the neck-in, the wider the effective product width, and the better the extrusion laminating processability.

Physical properties of laminate
Drop bag impact test
The obtained laminated film is cut into a size of MD 140 mm × TD 170 mm, the MDs are aligned, and the biaxially stretched polypropylene film surface is placed outside, and the MD 2 side and the TD 1 side are 10 mm wide. The test bag was obtained by thermocompression bonding (conditions: 200 ° C., 2 kg / cm ² , 1.0 second). It was then filled with 250 ml of tap water. Then, the remaining TD 1 side was also thermocompression-bonded in the same manner with a width of 10 mm to obtain a tap water filling test bag.

  The obtained tap water filling test bag was stored refrigerated at 3 ° C. for one week. After 20 consecutive vertical drops from a height of 120 cm above the concrete floor, with the final sealed part (one side sealed last) up, the samples after cold storage were checked for presence or absence of bags . The experiment is performed on a plurality of samples, and the evaluation result is expressed as "the number of broken bags / n (n: the number of bags used in the falling bag test)".

<Impact resistance>
A film test piece is fixed to a holder with a diameter of 50 mm using a film subjected to retort sterilization by the above method using an apparatus in accordance with JIS P8134 at an ambient temperature of 0 ° C., and a 25.4 mm hemispherical metal penetrating portion The amount of work (J) required for the penetration fracture was measured and divided by the film thickness.

[Used resin]
The propylene polymers (X-1) to (X-3) produced in Production Examples 1 to 3 described later were used as propylene polymers (X) used in Examples and Comparative Examples.

  As the propylene-ethylene block copolymer (Y), propylene-ethylene block copolymers (Y-1) to (Y-4) produced in the following production examples (Y-1) to (Y-4) and (Y-5) was used.

Moreover, the following Y-5 was used as a propylene homopolymer.
Y-5:
Nippon Polypropylene Corporation, trade name "Novatec (registered trademark) SA1"
Ziegler-Natta catalyzed propylene homopolymer MFR = 25, Tm = 158 ° C

Moreover, the following LDPE-1 was used as low density polyethylene.
LDPE-1;
Asahi Kasei Chemicals L6810
MFR = 10.5 (190 ° C, 2.16 kg load), Tm = 107 ° C

[Production Example 1: Production of Propylene-Based Polymer X-1]
Synthesis Example 1 of Catalyst Component [A-1]
(1) Synthesis of dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium: (component [A-1] (Synthesis of Complex 1):
(1-1) Synthesis of 4- (4-i-propylphenyl) indene:
In a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) are added, a solution of 90 g (0.28 mol) of cesium carbonate and 100 ml of water is added, 4-bromoindene 13 g (67 mmol) and 5 g (4 mmol) of tetrakistriphenyl phosphino palladium were sequentially added, and heated at 80 ° C. for 6 hours.
After cooling, 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 brine and dried over sodium sulfate. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified through a silica gel column to obtain 15.4 g (yield 99%) of a colorless liquid of 4- (4-i-propylphenyl) indene.

Synthesis of (1-2) 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 and 200 ml of DMSO were added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. . The mixture was stirred at room temperature for 2 hours, the reaction solution was 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 water. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified through a silica gel column to obtain 19.8 g (yield 96%) of a yellow liquid of 2-bromo-4- (4-i-propylphenyl) indene. .

Synthesis of (1-3) 2- (2-Methyl-5-furyl) -4- (4-i-propylphenyl) indene:
6.7 g (82 ml) of 2-methylfuran and 100 ml of DME were added to a 500 ml glass reaction vessel, and cooled to -70 ° C with a dry ice-methanol bath. 51 ml (81 mmol) of 1.59 mol / L n-butyllithium n-hexane solution was dripped here, and it stirred as it is for 3 hours. It cooled to -70 degreeC, and the solution of 20 ml (87 mmol) of triisopropyl borates and 50 ml of DME was dripped there. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After 50 ml of distilled water was added to the reaction solution for hydrolysis, a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 gg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were sequentially added, and the mixture was heated at 80 ° C. The mixture was heated and reacted for 3 hours while removing low boiling components. After cooling, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel, extracted three times with diisopropyl ether, the ether layer was washed with saturated brine and dried over sodium sulfate. The sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and the residue is purified through a silica gel column to obtain 19.6 g of a colorless liquid of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene ( The yield is 99%).

Synthesis of (1-4) Dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane:
In a 500 ml glass reaction vessel, 9.1 g (29 mmol) of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene and 200 ml of THF are added, and -70 in a dry ice-methanol bath. It cooled to ° C. 17 ml (28 mmol) of 1.66 mol / L n-butyllithium-hexane solutions were dripped here, and it stirred as it is for 3 hours. It cooled to -70 degreeC, 0.1 ml (2 mmol) of 1-methyl imidazole and 1.8 g (14 mmol) of dimethyldichlorosilanes were added in order, and it stirred overnight, returning gradually to room temperature.
Distilled water was added to the reaction solution, the mixture was transferred to a separatory funnel, washed with brine until neutral, sodium sulfate was added, and the reaction solution was dried. The sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and the residue is purified through a silica gel column to obtain dimethyl bis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane. 8.6 g (yield 88%) of a yellow solid were obtained.

Synthesis of (1-5) Dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride:
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 to dry. It cooled to -70 degreeC with an ice-methanol bath. To this, 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred for 3 hours. The solvent of the reaction mixture was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the mixture was cooled to -70 ° C with a dry ice-methanol bath. Thereto, 4.0 g (13 mmol) of hafnium tetrachloride was added. Then, it stirred overnight, gradually returning to room temperature.

The solvent is distilled off under reduced pressure, recrystallization is carried out with dichloromethane-hexane, and the racemate of dimethylsilylene bis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride is obtained. 7.6 g (yield 65%) were obtained as yellow crystals.
The identification value by < ¹ > H-NMR about the obtained racemate is described below.
¹ H-NMR (C6D6) identification results Racemate: δ 0.95 (s, 6 H), δ 1.10 (d, 12 H), δ 2.08 (s, 6 H), δ 2.67 (m, 2 H), δ 5. 80 (d, 2 H), δ 6. 37 (d, 2 H), δ 6. 74 (dd, 2 H), δ 7.0 7 (d, 2 H), δ 7. 13 (d, 4 H), δ 7. 28 (s, 2 H) ), Δ 7.30 (d, 2H), δ 7.83 (d, 4H).

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

[Example of synthesis of catalyst component [B]]
Chemical treatment of ion exchange layered silicates:
In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then 400 g of montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., trade name Benclay SL: average particle diameter 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. for 210 minutes. When 4,000 g of distilled water was added to the reaction slurry and then filtered, 810 g of a cake-like solid was obtained.
Next, in a separable flask, 432 g of lithium sulfate and 1,924 g of distilled water were added to obtain a lithium sulfate aqueous solution, and the entire cake-like solid was charged. The slurry was allowed to react for 120 minutes at room temperature. After adding 4 L of distilled water to this slurry, it filtered, and also it wash | cleaned to pH 5-6 with distilled water, and when filtration was performed, 760 g of cake-like solid were obtained.
The resulting solid was predried overnight at 100 ° C. in a nitrogen stream, and then coarse particles of 53 μm or more were removed and further dried under reduced pressure at 200 ° C. for 2 hours 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].

[Catalyst preparation and prepolymerization]
In a three-necked flask (volume 1 L), 20 g of the chemically treated montmorillonite obtained above is placed, and heptane (132 mL) is added to form a slurry, to which triisobutylaluminum (25 mmol: heptane solution having a concentration of 143 mg / mL) is added. .0 mL) was added and the mixture was stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100, to make the total volume 100 mL.
In another flask (volume 200 mL), rac-dichloro [1,1′-dimethylsilylene bis {2- (5-methyl-2-furyl) prepared in Synthesis Example 1 of the catalyst component [A-1]. ) (4- (4-i-propylphenyl) indenyl)] hafnium (210 μmol) is dissolved in toluene (42 mL) (solution 1), and in a separate flask (volume 200 mL), the catalyst component [A- Dissolution of rac-dichloro [1,1′-dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium (90 μmol) prepared in Example 2 of 2] in toluene (18 mL) (Solution 2).

The triisobutylaluminum (0.84 mmol: 1.2 mL of heptane solution with a concentration of 143 mg / mL) was added to the 1 L flask containing the previously-treated chemically treated montmorillonite, then the 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 further added, the above solution 2 was added, and the mixture was stirred at room temperature for 1 hour.
Then, 338 mL of heptanes were added and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was brought to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was carried out while maintaining the temperature at 40 ° C. for 4 hours. After that, the propylene feed was stopped, and the remaining polymerization was performed for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 17.0 mL of heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
The solid was dried under reduced pressure for 1 hour to obtain 56.4 g of a dry prepolymerized catalyst. The prepolymerization ratio (the value obtained by dividing the prepolymerization polymer amount by the solid catalyst amount) was 1.82 (prepolymerization catalyst 1).

[Polymerization Example 1]
After sufficiently replacing the inside of a 200-liter stirred type autoclave with propylene, 45 kg of fully dehydrated liquefied propylene was introduced. To this, 7.0 NL (0.63 g) of hydrogen and 0.54 kg of ethylene were added, and after adding triisobutylaluminum (0.12 mol: 0.47 L of heptane solution with a concentration of 50 g / L), the internal temperature was 70 ° C. The temperature rose to the end. Then, 1.9 g of 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, the unreacted monomer was purged, and the polymerization was terminated by purging the autoclave with nitrogen.
The obtained polymer was dried under a nitrogen stream at 90 ° C. for 1 hour to obtain 22.3 kg of a polymer.
The catalyst activity was 11700 g PP / g catalyst. The MFR was 6.7 g / 10 min (dg / min), and the ethylene content in the polymer was 0.92 wt%.

[Production Example 2: Production of Propylene-Based Polymer X-2]
Polymerization Example 2
The procedure of polymerization example 1 was repeated except that the amount of hydrogen to be added was 4.7 NL (0.42 g) and the amount of ethylene was 0.56 kg. As a result, 20.1 kg of a polymer was obtained.
The catalyst activity was 10600 g PP / g catalyst. The MFR was 2.1 g / 10 min (dg / min), and the ethylene content in the polymer was 0.93 wt%.

Production Example 3 Production of Propylene-Based Polymer X-2
[Polymerization Example 3]
The same procedure as in polymerization example 1 was carried out except that 7.5 NL (0.67 g) of hydrogen to be added, 0.56 kg of ethylene and 1.5 g of the prepolymerization catalyst 1 used were used. As a result, 19.9 kg of a polymer was obtained.
The catalyst activity was 13300 g PP / g catalyst. The MFR was 9.7 g / 10 min (dg / min), and the ethylene content in the polymer was 0.95 wt%.

[Production of Pellets (X-1) to (X-3) of Propylene-Based Polymers (X-1) to (X-3)]
100 parts by weight of the propylene-based polymers (X-1) to (X-3) produced in Production Examples 1 to 3 is tetrakis [methylene-3- (3 ′, 5 ′), which is a phenol-based antioxidant. -Di-t-butyl-4'-hydroxyphenyl) propionate] methane (trade name “IRGANOX 1010”, manufactured by BASF Japan Ltd.) 0.125 parts by weight, tris (2, 4 as a phosphite antioxidant) 0.125 parts by weight of -di-t-butylphenyl) phosphite (trade name "IRGAFOS 168", manufactured by BASF Japan Ltd.) and blended at a room temperature using a high-speed stirring mixer (Henshell mixer-trade name) The mixture was mixed for 3 minutes and then melt-kneaded with a twin-screw extruder to obtain pellets (X-1) to (X-5) of a propylene-based polymer (X).
Note that KZW-25 manufactured by Technobel Co., Ltd. is used for the twin-screw extruder, the screw rotation speed is 400 RPM, and the kneading temperature is set to 80, 160, 210, 230 from below the hopper (hereinafter the same temperature to the die exit) ° C did.

Evaluation of ethylene content, MFR, Mw / Mn, GPC molecular weight of 2,000,000 or more, TREF 40 ° C. or less, elution amount, mm, λmax, ME, α / β for these pellets (X-1) to (X-3) Did.
The evaluation results are shown in Table 1.

[Y Production Examples 1 to 4 (Production of Propylene-Ethylene Block Copolymer Y-1 to 4)]
[Y Production Example 1 Catalyst Synthesis]
(1) Preparation of Solid Component A 10 L autoclave equipped with a stirrer was sufficiently purged with nitrogen, and 2 L of purified toluene was introduced. Here, 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added at room temperature. The temperature was raised to 90 ° C., and 40 ml of di-n-butyl phthalate and 10 ml of di-ethyl phthalate were introduced. Thereafter, the temperature was raised to 110 ° C. and reaction was performed for 3 hours. The reaction product was thoroughly washed with purified toluene.
Then, purified toluene was introduced to adjust the total liquid volume to 2 liters. At room temperature, 1 L of TiCl ₄ was added, and the temperature was raised to 110 ° C. to carry out a 2 hr reaction. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 liters. At room temperature, 1 L of TiCl ₄ was added, and the temperature was raised to 110 ° C. to carry out a 2 hr reaction. The reaction product was thoroughly washed with purified toluene. Further, toluene was replaced with n-heptane using purified n-heptane to obtain a slurry of solid components. A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component was 1.7% by mass.
Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g (0.036 mol Ti) of the above solid component slurry was introduced as a solid component. The purified n-heptane was introduced to adjust the concentration of the solid component to 25 g / L. 50 ml of SiCl ₄ was added and reaction was carried out at 90 ° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and then the purified n-heptane was introduced to adjust the liquid level to 4 liters. Here, _[CH 2 = _CH] The _{2 -SiMe 2 25ml, (i-} Pr) and ₂ Si _(OMe) 2 18ml, the n- heptane dilution of triethylaluminum 40 g (0.35 mol) added as triethylaluminum The reaction was carried out at 40 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane, and a part of the obtained slurry was sampled and dried.
As a result of analysis, the solid component contained 0.9% by mass of Ti and 6.7% by mass of (i-Pr) ₂ Si (OMe) ₂ .

(2) Prepolymerization The prepolymerization was performed according to the following procedure using 100 g (0.019 mol Ti) of the solid component obtained above.
The purified n-heptane was introduced into the above slurry to adjust the concentration of the solid component to 20 g / L. After the slurry was cooled to 10 ° C., 15 g (0.132 mol) of triethylaluminum diluted with n-heptane as triethylaluminum was added, and 280 g of propylene was fed over 4 hours. The reaction was continued for another 30 minutes after the supply of propylene was completed.
Then, the gas phase was thoroughly replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was withdrawn from the autoclave and vacuum dried to obtain a solid catalyst component.
The solid catalyst component contained 2.0 grams of polypropylene per gram of solid component. As a result of analysis, 0.8% by mass of Ti and 6.4% by mass of (i-Pr) ₂ Si (OMe) ₂ were contained in the solid catalyst component (b) excluding the polypropylene.

(3) Production of propylene-based block copolymer
[Y Production Example 1 Polymerization]
First step The 3 L autoclave was previously dried well by circulating nitrogen under heating, then the inside of the tank was replaced with propylene and cooled to room temperature. Thereafter, 400 mg of triethylaluminum, 9400 NmL of hydrogen and 750 g of propylene were introduced. When the temperature in the tank was kept at 70 ° C., 3.0 mg of the solid catalyst component obtained above except for the prepolymer was injected by using 3.0 mg of high pressure argon to start the first stage polymerization. did. The temperature in the system was maintained at 70 ° C. during the polymerization of the first step.
After one hour, unreacted propylene in the system was purged, and the system was purged with nitrogen by repeating pressure increase and decrease using nitrogen to stop the reaction.
From the nitrogen-substituted autoclave, 10 g of the polymer after the first step was recovered and analyzed using a Teflon (registered trademark) tube.
Second Step Thereafter, the above-mentioned nitrogen substituted autoclave was kept at atmospheric pressure at 75 ° C., then hydrogen, propylene and then ethylene were quickly added to start the polymerization of the second step. During the polymerization, a mixed gas of ethylene / propylene, which was previously adjusted to have a constant composition, was introduced to maintain the total pressure at 1.9 MPa and maintain 75 ° C. The average gas composition of this second step polymerization was 25 mol% C ₂ H _{4 and} 5 mol% H ₂ .
Thereafter, the unreacted mixed gas in the system was purged, and nitrogen substitution was repeated to stop the second stage reaction. The autoclave was opened to obtain 305 g of a propylene-based polymer.
The obtained polymer measured various indexes using the said analysis method. The results are shown in Table 2.

[Y Production Example 2 Polymerization]
First step The 3 L autoclave was previously dried well by circulating nitrogen under heating, then the inside of the tank was replaced with propylene and cooled to room temperature. Thereafter, 400 mg of triethylaluminum, 4800 NmL of hydrogen and 750 g of propylene were introduced. When the temperature in the tank was kept at 70 ° C., 3.5 mg of the solid catalyst component obtained in Y Preparation Example 1 was injected by using high pressure argon at a value excluding the prepolymer, using the first stage. The polymerization was initiated. The temperature in the system was maintained at 70 ° C. during the polymerization of the first step.
After one hour, unreacted propylene in the system was purged, and the system was purged with nitrogen by repeating pressure increase and decrease using nitrogen to stop the reaction.
From the nitrogen-substituted autoclave, 10 g of the polymer after the first step was recovered and analyzed using a Teflon (registered trademark) tube.
Second Step Thereafter, the above-mentioned nitrogen substituted autoclave was kept at atmospheric pressure at 75 ° C., then hydrogen, propylene and then ethylene were quickly added to start the polymerization of the second step. During the polymerization, a mixed gas of ethylene / propylene, which was previously adjusted to have a constant composition, was introduced to maintain the total pressure at 1.9 MPa and maintain 75 ° C. The average gas composition of the polymerization in the second step was 55 mol% C ₂ H _{4 and} 5 mol% H ₂ .
Thereafter, the unreacted mixed gas in the system was purged, and nitrogen substitution was repeated to stop the second stage reaction. By opening the autoclave, 198 g of a propylene-based polymer was obtained.
The obtained polymer measured various indexes using the said analysis method. The results are shown in Table 2.

[Y Preparation Example 3 Synthesis of Catalyst]
Synthesis of dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride (metallocene compound A) 4- (4-t-butylphenyl)- Synthesis of Indene In a 1000 ml glass reaction vessel, 40 g (0.19 mol) of 1-bromo-4-t-butyl-benzene and 400 ml of dimethoxyethane (DME) were added and cooled to -70 ° C in a dry ice-methanol bath . To this was added dropwise 260 ml (0.38 mol) of a 1.46 mol / L t-butyllithium-pentane solution. After dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, and 100 ml of a DME solution containing 46 ml (0.20 mol) of triisopropyl borate was dropped there. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After adding 100 ml of distilled water to the reaction solution and stirring for 30 minutes, an aqueous solution of 50 g of sodium carbonate-150 ml of distilled water, 30 g (0.15 mol) of 4-bromoindene, 5 g (4.3 mmol) of tetrakis (triphenylphosphino) palladium Were sequentially added, after which the low boiling components were removed and heated at 80.degree.
The reaction solution was poured into 1 L of ice water, ether extraction was performed 3 times from there, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added to this, and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified through a silica gel column to obtain 37 g (yield 98%) of 4- (4-t-butylphenyl) -indene as a pale yellow liquid.

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

Synthesis of 2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indene Into a 1000 ml glass reaction vessel, 13.8 g (0.17 mol) of methylfuran and 400 ml of DME were added. It cooled to -70 degreeC with the dry ice methanol bath. Here, 111 ml (0.17 mol) of a 1.52 mol / L n-butyllithium-hexane solution was dropped. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, and 100 ml of a DME solution containing 41 ml (0.18 mol) of triisopropyl borate was dropped there. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After adding 50 ml of distilled water to the reaction solution and stirring for 30 minutes, sodium carbonate 54 g-distilled water 100 ml aqueous solution, 2-bromo-4- (4-t-butylphenyl) -indene 46 g (0.14 mol), tetrakis 5 g (4.3 mmol) of phenylphosphino) palladium were sequentially added, and the mixture was heated while removing low boiling components and heated at 80 ° C. for 3 h.
The reaction solution was poured into 1 L of ice water, ether extraction was performed 3 times from there, and the ether layer was washed with saturated brine until neutral. Sodium sulfate was added to this, and left overnight to dry the reaction solution. Anhydrous sodium sulfate is filtered, the solvent is distilled off under reduced pressure, the residue is purified by silica gel column, recrystallized with hexane and 2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) 30.7 g (yield 66%) of indene are obtained as colorless crystals.

Synthesis of Dimethylbis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) silane In a 1000 ml glass reaction vessel, 2- (2- (5-methylfuryl) )) 4- (4-t-Butylphenyl) -indene 22 g (66 mmol), 200 ml of THF were added, and cooled to -70 ° C with a dry ice-methanol bath. 42 ml (67 mmol) of 1.60 mol / L n-butyllithium-hexane solutions were dripped here. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, 0.3 ml (3.8 mmol) of 1-methylimidazole was added, and 100 ml of a THF solution containing 4.3 g (33 mmol) of dimethyldichlorosilane was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Sodium sulfate was added to this, and left overnight to dry the reaction solution. Anhydrous sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and purification on a silica gel column is carried out to obtain dimethyl bis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl). 22 g (yield 92%) of a pale yellow solid of silane was obtained.

Synthesis of dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride In a 300 ml glass reaction vessel, dimethyl bis (2- (2- (2- (2-methylphenyl)) was added. 11 g (16 mmol) of (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) silane and 200 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. To this, 20 ml (32 mmol) of a 1.60 mol / L n-butyllithium-hexane solution was dropped. After dropping, the temperature was returned to room temperature and stirred for 3 hours. The solvent of the reaction mixture was distilled off under reduced pressure, 200 ml of toluene and 10 ml of diethyl ether were added, and the mixture was cooled to -70 ° C with a dry ice-methanol bath. Thereto, 3.7 g (16 mmol) of zirconium tetrachloride was added. Then, it stirred overnight, gradually returning to room temperature.
The solvent is distilled off under reduced pressure, recrystallization is carried out with dichloromethane / hexane, and dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride The racemic mixture (purity 99% or more) of compound A) was obtained as yellow-orange crystals in 1.3 g (yield 9%).
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.14 (s, 6 H), δ 1.33 (s, 18 H), δ 2.41 (s, 6 H), δ 6.05 (d, 2 H), δ 6. 27 (d, 2 H), δ 6. 80 (dd, 2 H), δ 6. 92 (d, 2 H), δ 7.08 (s, 2 H), δ 7.31 (d, 2 H), δ 7.44 (d, 4 H) ), Δ 7.58 (d, 4 H).

Chemical treatment (acid treatment and salt treatment) of smectite group ion-exchanged layered silicate
Acid treatment: 1130 g of distilled water and 750 g of 96% sulfuric acid are added to a separable flask, the internal temperature is maintained at 90 ° C., and Benklay SL (average particle diameter 19 μm, 300 g) manufactured by Mizusawa Chemical Co., Ltd. granulated montmorillonite is added thereto. It was processed for 2 hours. The suspension was cooled to room temperature for 1 hour and washed with distilled water. The washing ratio at this time was 1/10000 or less.
Salt treatment: 210 g of lithium sulfate monohydrate was dissolved in 520 g of distilled water in a separable flask, and filtered acid-treated clay was added thereto and stirred at room temperature for 120 minutes. The slurry was filtered, and 3000 ml of distilled water was added to the obtained solid, and stirred at room temperature for 5 minutes. The slurry was filtered. Distilled water 2500 ml was added to the obtained solid, and it filtered again after stirring for 5 minutes. This operation is further repeated four times, and the obtained solid is predried at 130 ° C. for 2 days under a nitrogen stream, then coarse particles of 53 μm or more are removed, and the chemically treated montmorillonite is further dried at 200 ° C. for 2 hours under reduced pressure. Obtained.

Catalyst preparation using metallocene compound A (catalyst A)
10.0 g of the chemically treated montmorillonite obtained above was weighed into a 1 L flask and added with 65 ml of heptane and 35 ml (25 mmol) of a heptane solution of triisobutylaluminum, and stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual ratio of 1/100, and finally the slurry amount was adjusted to 50 ml. To this, 3.3 ml (2.4 mmol) of a heptane solution of triisobutylaluminum was added and stirred for 10 minutes at room temperature. Further, a solution of 223 mg (293 μmol) of metallocene compound A in 60 ml of toluene was added and stirred at room temperature for 60 minutes.
Next, 340 ml of heptane was added to the above heptane slurry and introduced into a 1 L internal volume stirring type autoclave, and propylene was supplied at a constant rate of 10 g / hour for 120 minutes at 40 ° C. After the propylene supply was completed, the temperature was raised to 50 ° C. and maintained for 2 hours. Thereafter, the residual gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand and the supernatant was withdrawn. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 30.5 g of a solid catalyst. The prepolymerization ratio (the value obtained by dividing the prepolymerization polymer amount by the solid catalyst amount) was 1.96.

[Y Production Example 3 Polymerization]
Propylene-propylene • ethylene block copolymerization by catalyst A First step: 2.76 ml (2.02 mmol) of a solution of triisobutylaluminum in n-heptane after sufficient substitution of propylene in the interior volume of 3 L of the stirring type autoclave with propylene ) Was added, and then 400 ml of hydrogen and then 750 g of liquid propylene were introduced, and the temperature was raised by maintaining the temperature at 65.degree. Catalyst A was slurried in n-heptane, and 20 mg of catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature in the tank was maintained at 65 ° C., and one hour after the addition of the catalyst, the remaining monomer was purged, and the inside of the tank was replaced with argon.
Second step: Thereafter, propylene was introduced to 0.76 MPa at an internal temperature of 60 ° C., subsequently ethylene was introduced to 1.8 MPa, and the internal temperature was raised to 80 ° C. Then, the polymerization reaction was controlled for 1 hour, adjusting the internal pressure to be 2.0 MPa while introducing a mixed gas of propylene and ethylene prepared in advance. As a result, 332 g of a propylene-propylene-ethylene block copolymer having good particle properties was obtained, and the MFR was 20 (dg / min). The average gas molar composition in the tank at the time of propylene and ethylene polymerization was propylene / ethylene = 49/51.
The obtained polymer measured various indexes using the said analysis method. The results are shown in Table 2.

[Y Production Example 4 Polymerization]
Propylene-Propylene-Ethylene Block Copolymerization by Catalyst A In the first step, 30 mg of catalyst A was used, and 324 ml of hydrogen was added. Operation was performed in the same manner as in Y Production Example 3 except that the average gas molar composition in the tank during propylene / ethylene polymerization in the second step was adjusted to be propylene / ethylene = 28/72, and the polymerization reaction was controlled for 20 minutes. did. As a result, 325 g of a propylene-propylene-ethylene block copolymer was obtained.
The obtained polymer measured various indexes using the said analysis method. The results are shown in Table 2.

Example 1
After mixing 10 parts by weight of X-2 and 90 parts by weight of Y-1 with a Henschel mixer (trade name), the mixture was melt-extruded at a temperature of 220 ° C. in an extruder with a screw diameter of 30 mmφ to pelletize. The obtained pellet was extruded at a resin temperature of 290 ° C. from a T-die of 300 mm in width attached to an extruder with a bore of 35 mm, and laminated on a 20 μm thick biaxially stretched polypropylene film at a thickness of 20 μm at a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that the ratio of X-2 to Y-1 was changed to 20 parts by weight and 80 parts by weight.
The quality of the obtained laminate was evaluated.

(Example 3)
A laminate was obtained in the same manner as in Example 1 except that the ratio of X-2 to Y-1 was changed to 40 parts by weight and 60 parts by weight.
The quality of the obtained laminate was evaluated.

(Example 4)
After mixing 20 parts by weight of X-1 and 80 parts by weight of Y-1 with a Henschel mixer (trade name), the mixture was melt extruded and pelletized at a temperature of 220 ° C. in an extruder with a screw diameter of 30 mmφ. The obtained pellet was extruded at a resin temperature of 290 ° C. from a T-die of 300 mm in width attached to an extruder with a bore of 35 mm, and laminated on a 20 μm thick biaxially stretched polypropylene film at a thickness of 20 μm at a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Example 5)
X-3: 30 parts by weight and Y-1: 70 parts by weight are mixed in the same manner as in Example 1, and then melt-extruded and pelletized, and the obtained pellet is attached to an extruder of 35 mm in diameter, 300 mm in width From a T-die, it was extruded at a resin temperature of 290 ° C. and laminated on a 20 μm thick biaxially oriented polypropylene film at a thickness of 20 μm and a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Example 6)
X-2: 20 parts by weight and Y-2: 80 parts by weight were mixed in the same manner as in Example 1, and then melt-extruded and pelletized, and the obtained pellet was attached to an extruder of 35 mm in diameter, 300 mm wide From a T-die, it was extruded at a resin temperature of 290 ° C. and laminated on a 20 μm thick biaxially oriented polypropylene film at a thickness of 20 μm and a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Example 7)
X-2: 20 parts by weight and Y-3: 80 parts by weight were mixed in the same manner as in Example 1, and then melt-extruded and pelletized, and the obtained pellet was attached to an extruder of 35 mm in diameter 400 mm wide From a T-die, it was extruded at a resin temperature of 290 ° C. and laminated on a 20 μm thick biaxially oriented polypropylene film at a thickness of 15 μm and a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Example 8)
After mixing 20 parts by weight of X-2 and 80 parts by weight of Y-4 with a Henschel mixer (trade name), the mixture was melt-extruded at a temperature of 220 ° C. in an extruder with a screw diameter of 30 mm and pelletized. The obtained pellet was extruded at a resin temperature of 290 ° C. from a T-die of 300 mm in width attached to an extruder with a bore of 35 mm, and laminated on a 20 μm thick biaxially stretched polypropylene film at a thickness of 15 μm at a speed of 10 m / min.
The quality of the obtained laminate was evaluated.

(Comparative example 1)
X-3: 100 parts by volume were extruded at a resin temperature of 290 ° C. from a 300 mm wide T-die attached to an extruder with a 35 mm aperture, and laminated on a 20 μm thick biaxially oriented polypropylene film at a thickness of 15 μm and a speed of 10 m / min However, surging was severe at 10 m / min and no film could be formed.

(Comparative example 2)
Y-1: 100 parts by volume were extruded at a resin temperature of 290 ° C from a 300 mm wide T-die attached to an extruder with a 35 mm aperture, and laminated on a 20 μm thick biaxially stretched polypropylene film at a thickness of 15 μm and a speed of 10 m / min did.
The quality of the obtained laminate was evaluated.

(Comparative example 3)
100 parts by weight is extruded at a resin temperature of 290 ° C. from a 300 mm wide T-die attached to an extruder with a 35 mm bore diameter, laminated on a 20 μm thick biaxially oriented polypropylene film at a thickness of 15 μm and a speed of 10 m / min However, surging was severe at 10 m / min and no film could be formed.

(Comparative example 4)
After mixing 90 parts by weight of Y-5 and 10 parts by weight of LDPE-1 with a Henschel mixer (trade name), the mixture was melt-extruded at a temperature of 220 ° C. in an extruder with a screw diameter of 30 mm and pelletized. The obtained pellet was extruded at a resin temperature of 290 ° C. from a T-die of 300 mm in width attached to an extruder with a bore of 35 mm, and laminated on a 20 μm thick biaxially stretched polypropylene film at a thickness of 15 μm at a speed of 10 m / min.
The quality of the obtained laminate was evaluated.
These evaluation results are summarized in Table 3.

[Discussion of Results of Examples and Comparative Examples]
As is clear from Examples 1 to 8 in Table 3, the polypropylene resin composition for laminating according to the present invention has high spreadability and small neck-in, while maintaining the anti-fall bag resistance and the impact resistance. It can be seen that the processability is improved.
On the other hand, when only the propylene-based polymer (X) having a branched structure was used, film formation could not be performed (Comparative Example 1). Moreover, when only a propylene ethylene block copolymer (Y) is used, it is not preferable because the neck-in is large and the spreadability is too low (Comparative Example 2). Furthermore, when only a propylene homopolymer was used, it was not able to form a film (comparative example 3). And when a propylene homopolymer and low density polyethylene are used, although the neck-in is small and the lamination processability is excellent and the spreadability is high, the lamination using the high speed extrusion processability is also possible. The body is not preferable because it is inferior in drop bag resistance and impact resistance (Comparative Example 4).

  The polypropylene-based resin composition for extrusion lamination of the present invention has a small neck-in and is excellent in laminating processability, and is also excellent in extrusion laminating processability at high speed because of high spreadability, and a laminate using this Since it is excellent in drop bag resistance and impact resistance, it can be suitably used for packaging applications such as various foods and beverages, medicines and medical products, cosmetics, clothing, stationery and other industrial materials and industrial materials The availability is extremely high.

Claims (11)

  Propylene polymer (X) 3 to 99 weight containing a total amount of ethylene and / or 1-butene as a comonomer at 10.0 mol% or less and having a strain hardening degree (λmax) of 1.1 or more in measurement of extensional viscosity %, And 1 to 97% by weight of a propylene-ethylene block copolymer (Y) comprising a propylene-based polymer component (A) and a propylene-ethylene random copolymer component (B) Polypropylene resin composition.   Propylene polymer (X) 3 to 99% by weight containing ethylene and / or 1-butene in a total amount of 10.0 mol% or less as a comonomer, propylene polymer component (A) and propylene-ethylene random copolymer For extrusion lamination characterized in that it comprises 1 to 97% by weight of a propylene-ethylene block copolymer (Y) consisting of the component (B), and the strain hardening degree (λmax) in measurement of extensional viscosity is 1.1 or more Polypropylene resin composition. The polypropylene-based resin composition for extrusion lamination according to claim 1 or 2, wherein the propylene-based polymer (X) satisfies the requirements defined in the following (i) to (iv).
(I) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 3.5 or more and 10.5 or less.
(Ii) In a molecular weight distribution curve obtained by GPC, the ratio of components having a molecular weight of 2,000,000 or more is 0.4% by weight or more and less than 10% by weight based on the total amount.
(Iii) In the temperature rising elution fractionation (TREF) with ortho-dichlorobenzene (ODCB), the component eluting at a temperature of 40 ° C. or less is 3.0 wt% or less.
(Iv) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 95% or more. The polypropylene-based resin composition for extrusion lamination according to any one of claims 1 to 3, wherein the propylene-based polymer (X) further satisfies the requirement defined in the following (v).
(V) ME (memory effect) and MFR (melt flow rate: 230 ° C., 2.16 kg load) satisfy the following equation.
(ME) − − 0.26 × log (MFR) + 1.9
[In the equation, ME (memory effect) uses a melt indexer with an orifice of 8.00 mm in length and 1.00 mm in diameter, sets the temperature in the cylinder to 190 ° C, applies a load, and the extrusion speed is 0 At 1 g / min, the polymer extruded from the orifice is quenched in ethanol, and the strand diameter of the extrudate at that time is divided by the orifice diameter. ] The polypropylene-based resin composition for extrusion lamination according to any one of claims 1 to 4, wherein the propylene-based polymer (X) further satisfies the requirement defined in the following (vi).
(Vi) in the molecular weight distribution curve obtained by GPC, the molecular weight of the common logarithm of Tp, a peak height of 50% of the height a position molecular weight logarithm and _{L 50} and _H 50 _{(L 50} corresponding to the peak position Tp lower molecular weight _{side, H 50} is a high molecular weight side) than Tp, alpha and beta, respectively α ₌ H 50 -Tp, when defining the _{β = Tp-L 50, α} / β is larger than 0.9, 2 Less than 0. Furthermore, the propylene-based polymer (X) satisfies the requirements defined in the following (vii), The polypropylene-based resin composition for extrusion lamination according to any one of claims 1 to 5.
(Vii) MFR (temperature 230 ° C., load 2.16 kg) is 0.1 g / 10 min or more and 30 g / 10 min or less.   The polypropylene resin composition for extrusion laminating according to any one of claims 1 to 6, wherein MFR of the propylene-ethylene block copolymer (Y) is 1 to 50 g / 10 min. The propylene-ethylene block copolymer (Y) is a propylene-ethylene block copolymer satisfying the conditions (viii) to (x) below: The polypropylene resin composition for extrusion lamination as described.
(Viii) The melting peak temperature Tm (A) of the propylene polymer component (A) is 150 to 165 ° C.
(Ix) The ratio [W (B)] of the propylene-ethylene random copolymer component (B) to the total amount of the propylene-ethylene block copolymer (Y) is 10 to 50% by weight.
(X) The ethylene content [E (B)] of the propylene-ethylene block copolymer component (B) is 10 to 85% by weight. The propylene-ethylene block copolymer (Y) is a metallocene- based propylene-ethylene block copolymer, The polypropylene resin composition for extrusion laminating according to any one of claims 1 to 8, characterized in that An extrusion laminate laminate, wherein the polypropylene resin composition according to any one of claims 1 to 9 is laminated on a substrate. How to use flop propylene-based polymer according to (X) to the extrusion laminated to claim 1 or 2, characterized by satisfying the requirements as set forth (i) ~ (vii) in claim 3-6.

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