JP2003206325A - Propylenic block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic block copolymer with favorable balances between rigidity and impact resistance for molding materials, with favorable heat resistance and moldability resulting in good appearance. <P>SOLUTION: The propylenic copolymer is prepared by a 1st step for preparation of a propylene polymer (PP) using a metallocene catalyst and a 2nd step for preparation of a propylene - ethylene copolymers (EP). The resultant block copolymer exhibits specific melt flow rate, PP and EP contents, molecular weight of highly crystalline polypropylene portion, and melting point. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based block copolymer containing polypropylene having a specific structure and an ethylene-propylene copolymer. More specifically, it relates to a propylene-based block copolymer which exhibits an extremely good rigidity-impact resistance balance when used as a molding material, has good heat resistance, and is excellent in moldability.

[0002]

2. Description of the Related Art Crystalline polypropylene has mechanical properties
It is widely used in various molding fields due to its excellent chemical resistance. However, when a propylene homopolymer is used as the crystalline polypropylene, the rigidity is increased but the impact resistance is insufficient. Therefore, by a method of adding an elastomer such as ethylene-propylene rubber to a propylene homopolymer, or a method of producing a so-called block copolymer by subsequently copolymerizing ethylene and propylene after homopolymerization of propylene, impact resistance is improved. Have been improved. Although the physical properties are considerably improved by these methods, it is desired to further improve the rigidity-impact resistance balance. Further, in addition to those characteristics, improvement for improving heat resistance is strongly desired.

On the other hand, it is known that isotactic polypropylene can be obtained by polymerizing propylene using a metallocene catalyst different from the conventional Ziegler type catalyst system. Further, after homopolymerization of propylene using the same catalyst, ethylene and propylene are subsequently copolymerized,
It is also known to produce a so-called block copolymer (see, for example, Patent Documents 1 to 5). Also, many examples of propylene-ethylene block copolymers having good rigidity and impact resistance have been proposed (see, for example, Patent Documents 6 to 9). Although the rigidity and impact resistance are further improved by the above invention, in addition to further improving the rigidity and impact resistance, it is also necessary to improve the heat resistance and the like, and the production is conducted using a metallocene catalyst. There is a need to ameliorate poor moldability due to the narrow molecular weight distribution which is a common property of polymers made. Generally a material with poor moldability,
It is known that when a large-sized molded article such as a bumper is injection-molded, a trasima-shaped molding appearance defect (flow mark) is caused, and such a defect causes a problem that the commercial property is deteriorated.

[Patent Document 1] Japanese Patent Laid-Open No. 4-337308

[Patent Document 2] JP-A-6-287257

[Patent Document 3] Japanese Patent Laid-Open No. 5-202152

[Patent Document 4] JP-A-6-206921

[Patent Document 5] Japanese Patent Laid-Open No. 10-219047

[Patent Document 6] Japanese Patent Laid-Open No. 11-228648

[Patent Document 7] Japanese Patent Laid-Open No. 11-240929

[Patent Document 8] Japanese Patent Laid-Open No. 11-349649

[Patent Document 9] Japanese Patent Laid-Open No. 11-349650

[0004]

That is, regarding the performance of the propylene-ethylene block copolymers exemplified in the above-mentioned prior art, although some improvement in impact resistance was observed, there is still room for improvement in heat resistance. In addition, there is almost no improvement effect on moldability. For this reason,
In the propylene block copolymer obtained by the conventional method, further improvement in the balance of rigidity-impact resistance, heat resistance and moldability, especially improvement in appearance such as flow marks has been a problem.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors to solve the above-mentioned problems in the prior art,
A propylene-based block copolymer containing a polypropylene having a specific structure and an ethylene-propylene copolymer having a specific structure in a specific ratio has a very good rigidity-impact resistance balance when used as a molding material. The present invention has been completed, and has been found to have high heat resistance and good moldability.

That is, the gist of the present invention is to use a metallocene catalyst to produce a propylene polymer component (PP) by a pre-stage process and a propylene-ethylene copolymer component (EP) by a post-stage process. A block copolymer, which is a propylene-based block copolymer characterized in that the block copolymer satisfies the following requirements (1) to (6). (1) Melt flow rate (MFR) is 0.1 to 15
It is 0 g / 10 minutes. (2) The propylene content of the component which is insoluble in ortho-dichlorobenzene at 100 ° C and soluble in ortho-dichlorobenzene at 140 ° C is 99.5% by weight or more. (3) Propylene in propylene block copolymer
The content of the ethylene copolymer component (EP) is 5 to 50% by weight. (4) The ethylene content (G) of EP is 15 to 65% by weight. (5) Mw / M, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the highly crystalline polypropylene component in the propylene block copolymer, which is determined by the cross fractionation method.
Let n be the Q value, and P be the common logarithm of the molecular weight corresponding to the peak position of the molecular weight distribution curve of the high crystalline polypropylene component, and L and H (L is Lower molecular weight than peak molecular weight, H
Is higher than the peak molecular weight), and α and β are defined as α = HP and β = P−L, respectively, the Q value and α / β satisfy the following relationship. A) Q value ≧ 2.3 a) α / β ≧ 0.4 × Q value (6) The melting point of the block copolymer is 157 ° C. or higher.

Another gist of the present invention is that the above requirements (1)-
A propylene-based block copolymer satisfying (6) and also satisfying the following requirement (7). Requirement (7) Insoluble in ortho-dichlorobenzene at 100 ° C,
In addition, the sum of the content of 2,1-bond and the content of 1,3-bond in the component soluble in orthodichlorobenzene at 140 ° C. is 0.06 to 0.6 mol%. Still another subject matter of the present invention is a propylene block copolymer that satisfies the above requirements (1) to (6) and also satisfies the following requirement (8). Requirement (8) Insoluble in ortho-dichlorobenzene at 100 ° C,
In addition, the content of 1,3-bonds in the component soluble in orthodichlorobenzene at 140 ° C. is 0.06 to 0.6 mol%.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The propylene-based block copolymer of the present invention comprises a propylene-ethylene copolymer component (E) and a preceding step of producing a propylene polymer component (PP) using a metallocene catalyst.
A propylene-based block copolymer obtained by the latter step of producing P), wherein the block copolymer is
It is characterized by satisfying the following requirements (1) to (6). Requirement (1) Melt flow rate (MFR) The propylene block copolymer of the present invention needs to have an MFR in the range of 0.1 to 150 g / 10 minutes. Generally, the higher the molecular weight, the lower the MFR, and therefore the MFR is a rough standard for representing the magnitude of the molecular weight. If the MFR is less than 0.1 g / 10 minutes, the fluidity during resin molding will be too low and the molding efficiency will be low. Further, the entanglement of the molecular chains is too strong, and the spherulite growth rate is reduced, resulting in a decrease in crystallinity and a decrease in rigidity. On the contrary, if the MFR exceeds 150 g / 10 minutes, the molecular weight becomes too small and the impact strength decreases. Preferred MFR in the present invention
The range is preferably from 4 to 100 g / 10 minutes, particularly preferably from 5 to 50 g, from both aspects of moldability and material properties.
The range is / 10 minutes. Further, recently, market demands for high-speed molded products and thin-walled molded products (so-called high-flow products) have been increasing, and when providing such materials, MFR is 50 to 150 g / 10 minutes, particularly 70 to 150
It is preferably g / 10 minutes. Generally, hydrogen gas, which is a chain transfer agent, is used to adjust the MFR, but it can be controlled by the polymerization temperature, the polymerization pressure, the monomer / comonomer raw material composition ratio, and a combination thereof. Is. The control range of these conditions may vary depending on the type of catalyst used.

Requirement (2) Ortho-dichlorobenzene (OD
CB) Insoluble component The propylene-based block copolymer of the present invention is required to have a propylene content of 99.5% by weight or more which is insoluble in ODCB at 100 ° C and soluble in ODCB at 140 ° C. is there. Such a component can be obtained by homopolymerization (homopolymerization) of propylene in the first step or by copolymerizing the raw material gas composition so as to contain 0.5% by weight or less of α-olefin. The insoluble component is an ODC at 140 ° C., which is insoluble in ODCB at 100 ° C. and is obtained by using a known temperature rising column fractionation method.
B refers to a soluble component. The temperature-increasing column fractionation method is, for example, Macromolecules, Volume 21, Pages 314 to 319 (1
988).

The ODCB insoluble component at 100 ° C. defined in the present invention is measured as follows. That is, a glass bead carrier (80 to 100 mesh) is packed in a cylindrical column having a diameter of 50 mm and a height of 500 mm, and the temperature is maintained at 140 ° C. Next, the ODC of the sample melted at 140 ° C
200 mL of B solution (10 mg / mL) is introduced into the column. Then, the temperature of the column is increased to 40 ° C at 10 ° C /
Cool at a rate of temperature decrease over time. After holding at 40 ° C for 1 hour, 1
The column temperature is heated to 100 ° C. at a temperature rising rate of 0 ° C./hour and kept for 1 hour. The accuracy of column temperature control through a series of operations is ± 1 ° C.

Then, with the column temperature kept at 100 ° C., ODCB at 100 ° C. was applied at a flow rate of 20 mL / min to 80 ° C.
By flowing 0 mL, the components dissolved in ODCB at 100 ° C. existing in the column are eluted and collected. Then, the column temperature is increased to 140 ° C at a temperature increase rate of 10 ° C / min.
Up to 140 ° C. and left still at 140 ° C. for 1 hour, then 800 mL of a solvent (ODCB) at 140 ° C. is flown at a flow rate of 20 mL / min to make it insoluble in 100 ° C. ODCB and 140 ° C.
A component soluble in ODCB is eluted and collected. 10
The ODCB solution containing components that are insoluble in ODCB at 0 ° C. and soluble in ODCB at 140 ° C. is concentrated to 20 mL using an evaporator and then precipitated in 5 volumes of methanol. The precipitated polymer is collected by filtration and then dried in a vacuum dryer overnight. This is referred to as "100 in the present invention.
ODCB insoluble component at ° C ".

[0012] ODCB is a good solvent for polyolefins and has a high boiling point of 181 ° C. Therefore, it is used for solvent separation in a wide temperature range from low temperature to high temperature. O at 100 ° C
The fact that it is insoluble in DCB means that it is a polypropylene component having high crystallinity among the components constituting the block copolymer, and it is a high component remaining after removing the component having poor crystallinity from the propylene-based block copolymer. It has the meaning of extracting only crystalline components. The propylene content of the component being 99.5% by weight or more means that even if the component is homopolypropylene or a copolymer of propylene and α-olefin, it is extremely less than 0.5% by weight. It is meant to contain only small amounts of α-olefins. Therefore, the ODCB-insoluble component at 100 ° C. has high crystallinity, which means that it has the effect of increasing the rigidity of the propylene block copolymer. At 140 ° C, the polymer is completely dissolved, so a value of 140 ° C is an OD of 100 ° C.
It has the meaning that all the components insoluble in CB can be recovered and used for the analysis of the propylene content. In the present invention, if the propylene content of the above-mentioned ODCB-insoluble component is less than 99.5% by weight, rigidity and heat resistance are deteriorated, which is not preferable. The component is more preferably homopolypropylene in order to maintain high rigidity. Further, such a component is preferably contained in the propylene block copolymer in an amount of 45% by weight or more, and particularly 60 to 90% by weight.

Requirement (3) EP content in propylene block copolymer In the propylene block copolymer of the present invention, the weight ratio of the propylene-ethylene copolymer component in the propylene block copolymer is
It is necessary to be 5 to 50% by weight. In order to achieve this range, the weight of PP manufactured in the first step and the weight of EP manufactured in the second step may be set to a predetermined ratio.
In general, in a propylene-based block copolymer, the propylene-ethylene copolymer is a random copolymer, a substance having poor crystallinity and showing physical properties such as rubber is a main component, and a basic factor expressing impact strength. Becomes In the present invention, since the propylene-ethylene copolymer has high random copolymerizability, it exhibits excellent physical properties in a wide range of the EP content of 5 to 50% by weight. If the EP content is less than 5% by weight, the rubber-like portion is too small and the impact strength is lowered, whereas if it exceeds 50% by weight,
There is a problem that the rigidity is lowered due to too few crystalline parts. In the present invention, the preferable EP content is 8 to 4
The range is 0% by weight, particularly preferably 10 to 30% by weight. E in the propylene-based block copolymer of the present subject matter
The definition and measuring method of the P content will be described in more detail later.

Requirement (4) EP ethylene content (G) The propylene block copolymer of the present invention must have an ethylene content (G) in the EP of 15 to 65% by weight. Preferably, it is 20 to 55% by weight. The method of measuring G will be described later. G is a factor that affects the crystallinity and rubber properties of the propylene-ethylene copolymer. In particular, it has a great influence on impact resistance at low temperatures below room temperature, especially at extremely low temperatures such as -10 to -30 ° C. When G is less than 15% by weight, the glass transition temperature of EP rises,
There is an inconvenience that the impact strength at low temperature decreases. Also EP
A phenomenon occurs in which a part of the above is solubilized in PP that serves as a matrix, which causes a problem that rigidity and heat resistance decrease. On the other hand, when G exceeds 65% by weight, EP is not uniformly dispersed in PP and impact strength is lowered. The ethylene content (G) of EP can be controlled to a desired value within the range defined by the present invention by adjusting the composition ratio of the raw material gas in the propylene-ethylene block copolymer production step in the latter step. it can.

Requirement (5) Q value and the relationship between Q value and α / β The propylene block copolymer of the present invention is obtained by the cross fractionation method, and the weight average molecular weight of the high crystalline polypropylene component in the propylene block copolymer is determined. Let Mw / Mn, which is the ratio of (Mw) and number average molecular weight (Mn), be the Q value, and P be the common logarithm of the molecular weight corresponding to the peak position of the molecular weight distribution curve of the high crystalline polypropylene component, and 5 be the peak height.
The common logarithm of the molecular weight at the position of% height is defined as L and H (L
Is a lower molecular weight side than the peak molecular weight, H is a higher molecular weight side than the peak molecular weight), and α and β are respectively α = HP,
When defining β = P−L, it is necessary that the Q value and α / β satisfy the following relationship. A) Q value ≧ 2.3 a) α / β ≧ 0.4 × Q value

Generally, in injection molding, when the MFR is high, the moldability is improved, and the appearance defects such as flow marks are less likely to occur, but when the MFR is too high, the impact strength is lowered and the molding material cannot exhibit sufficient performance. . Further, if the MFR is lowered in order to increase the impact strength, the appearance defects such as flow marks become remarkable and the commercial value is impaired. Therefore, it has been required to maintain the MFR and impact strength constant and improve the moldability.

The high crystalline polypropylene component has a Q value of 2.3.
If it is smaller, the fluidity and moldability, especially the effect of improving the flow mark is not recognized, and even if the Q value is 2.3 or more, if the value of α / β is smaller than 0.4 × Q value. Even if the effect of improving the moldability is exhibited, the balance between rigidity and impact resistance is deteriorated.

The "highly crystalline polypropylene component" in the propylene block copolymer of the present invention means an OD of 100 ° C. when measured by a cross fractionation chromatograph as described later.
It is a component that does not elute with CB but dissolves and elutes in ODCB at 140 ° C. Among the propylene block copolymers of the present invention, the rubber component, atactic polypropylene component, component having crystallinity based on ethylene chain, and component not having high crystallinity among PP are all 10
It elutes at 0 ° C or lower, and at 140 ° C, only the highly crystalline polypropylene component elutes. In general, it is known that it is useful to widen the molecular weight distribution in order to improve the moldability, but as a result of intensive studies by the present inventors, the molecular weight of the high crystalline polypropylene component was improved to improve the moldability. We find that it is important to broaden the distribution. The Q value is a well-known parameter as an index of the breadth of the molecular weight distribution, and the larger the Q value, the wider the molecular weight distribution. As the Q value becomes smaller, the molecular weight distribution becomes narrower, which deteriorates the moldability and adversely affects the dispersibility of rubber. In particular, when the Q value is less than 2.3, the molecular weight distribution becomes too narrow and the moldability becomes extremely poor.

The Q value is a general index showing the breadth of the molecular weight distribution, but is not an index relating to the shape of the molecular weight distribution. According to the study of the present inventor, the mechanical properties of the propylene-based block copolymer, particularly the balance between rigidity and impact resistance, changes greatly depending on the shape of the molecular weight distribution curve of the high-crystalline propylene component, and if the Q value is increased, molding is performed. Although the property is improved, when the tailing to the low molecular weight side becomes severe as a result of increasing the Q value, the amount of the low molecular weight component, which is not preferable in terms of mechanical properties, increases, and the rigidity-impact resistance The balance gets worse. The highly crystalline propylene component forms a matrix component in the block copolymer, plays a role in the rigidity of the material, and is an important component that produces crazes by impact and absorbs energy. Therefore, in order to improve the moldability while maintaining good mechanical properties, it is important to suppress tailing to the low molecular weight side and widen it to the high molecular weight side when broadening the molecular weight distribution of the high crystalline propylene component. α / β
Is an index showing the ratio of the tailing strength to the high molecular weight side and the tailing strength to the low molecular weight side. The larger α / β, the larger the tailing to the higher molecular weight side,
On the contrary, the smaller α / β is, the more the tailing is on the low molecular weight side. In the case where the high molecular weight side and the low molecular weight side have the same degree of tailing, α / β becomes 1. Further, from the viewpoint of suppressing tailing to the low molecular weight side, α / β does not have to be a certain value or more. Increasing the Q value inevitably increases the amount of low-molecular weight components accordingly. Therefore, the larger the Q value, the larger the α / β ratio, and the more tailing to the higher molecular weight side is strengthened. An increase in the ratio of low molecular weight component to high molecular weight component must be suppressed. The necessary condition that should be satisfied by α / β and the Q value obtained empirically by the study of the present inventors is α / β ≧ 0.4 × Q value.

<Determination of Parameters of Requirements (3) to (5)> In the present invention, the EP content in the propylene block copolymer, the ethylene content (G) in the EP, and the highly crystalline propylene component. The Q values, α, and β of are determined by the following method.

1. Analyzing equipment used Cross sorting equipment Dia Instruments Co., Ltd. CFC T-100 (CF
Abbreviated as C) Fourier transform infrared absorption spectrum analysis FT-IR, fixed wavelength infrared spectrophotometer attached as a detector of Perkin Elmer 1760X CFC is removed and FT-IR is connected instead, This FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR has a length of 1 m, and is 1 throughout the measurement.
Hold temperature at 40 ° C. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ and is maintained at 140 ° C. throughout the measurement. Gel permeation chromatography (GPC) The GPC column in the latter part of CFC is AD8 manufactured by Showa Denko KK
Three 06MS are connected in series for use.

2. CFC measurement conditions Solvent: Orthodichlorobenzene (ODCB) Sample concentration: 4 mg / mL Injection volume: 0.4 mL Crystallization: The temperature is lowered from 140 ° C to 40 ° C over about 40 minutes. Separation method: Separation temperature at elevated temperature elution separation is 40, 10
The temperature is adjusted to 0 and 140 ° C., and fractionation is carried out into a total of 3 fractions. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3) was W, respectively. ₄₀ , W ₁₀₀ ,
It is defined as W _140. W ₄₀ + W ₁₀₀ + W ₁₄₀ = 100. The separated fractions are automatically transported to the FT-IR analyzer as they are after passing through the GPC column in the subsequent stage. Solvent flow rate during elution: 1 mL / min

3. FT-IR measurement conditions After starting the elution of the sample solution from GPC in the latter stage of CFC,
FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above fractions 1 to 3. A conceptual diagram of CFC-FT-IR is shown in FIG. Detector: MCT Resolution: 8 cm ^-1 Measurement interval: 0.2 minutes (12 seconds) Accumulation count per measurement: 15 times

4. Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are FT-
The absorbance at 2945 cm ^-1 obtained by IR is used as a chromatogram and determined. The elution amount is standardized so that the total elution amount of each elution component is 100%. The conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F2
0, F10, F4, F1, A5000, A2500, A
1000. ODCB (0.5
0.4 mL of a solution dissolved in BHT (containing 2,6-di-t-butyl-4-methylphenol) of mg / mL)
Inject to create a calibration curve. For the calibration curve, a cubic expression obtained by approximation by the least square method is used. Conversion to molecular weight is performed by Sadao Mori "Size Exclusion Chromatography" (Kyoritsu Publishing).
Use a general-purpose calibration curve as a reference. The following numerical values are used for the viscosity formula ([η] = K × Mα) used at that time. When preparing a calibration curve using standard polystyrene K = 0.000138, α = 0.70 When measuring a sample of a propylene-based block copolymer K = 0.00103, α = 0.78 Ethylene content distribution of each eluted component ( The distribution of ethylene content along the molecular weight axis) was determined by using the ratio of the absorbance at 2956 cm ^-1 and the absorbance at 2927 cm ^-1 obtained by GPC-IR, using polyethylene, polypropylene or ¹³ C-N
Converted to ethylene content (% by weight) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) whose ethylene content is known by MR measurement and the like and mixtures thereof. Ask.

<EP content> Propylene in the present invention
The EP content of the block copolymer is determined by the following formula (I).
And is required by the following procedure.   EP content (% by weight) = W₄₀× A₄₀/ B₄₀+ W₁₀₀× A₁₀₀/ B₁₀₀  (I) (W₄₀, W₁₀₀Is the elution ratio for each fraction described above.
(Unit: wt%), A₄₀, A₁₀₀Is W₄₀, W
₁₀₀The average error of the actual measurement in each fraction corresponding to
Tylene content (unit:% by weight), B₄₀, B
₁₀₀Is the ethylene content of EP contained in each fraction
The amount (unit:% by weight). A₄₀, A₁₀₀, B₄₀, B₁₀₀
How to obtain is described later. The meaning of the formula (I) is as follows.
It That is, the first term on the right side of the equation (I) is the fraction 1
Calculate the amount of EP contained in the (soluble part at 40 ° C)
Is a term. Fraction 1 contains only EP and not PP
If not, W₄₀Hula occupies the whole as it is
It contributes to the EP content derived from fraction 1, but the fraction
In addition to EP-derived components, a small amount of PP-derived components
(Extremely low molecular weight components and atactic polypropylene
(Lens) is also included, so that part needs to be corrected.
It So W₄₀To A₄₀/ B₄₀By multiplying
In the action 1, the amount derived from the EP component is calculated. example
If the average ethylene content of fraction 1 (A₄₀) Is 30
% By weight of EP contained in fraction 1
Content (B₄₀) Is 40% by weight, the fraction
30/40 = 3/4 (that is, 75% by weight) of EP 1 is due to EP
From now on, 1/4 will be derived from PP. Right like this
A in the first term ₄₀/ B₄₀The operation of multiplying the
Weight% (W₄₀) Means to calculate the EP contribution from
It The second term on the right-hand side is also the same, and
And the EP contribution is calculated and added.
It becomes a large amount.

(1) As described above, the average ethylene contents corresponding to the fractions 1 and 2 obtained by the CFC measurement are A ₄₀ and A ₁₀₀ , respectively (the unit is% by weight). The method for obtaining the average ethylene content will be described later. (2) Let B _{40 be the} ethylene content corresponding to the peak position in the molecular weight distribution curve of fraction 1 (see FIG. 2) (the unit is% by weight). With regard to the fraction 2, it is considered that the rubber portion is completely eluted at 40 ° C., and the same definition cannot be applied. Therefore, in the present invention, B ₁₀₀ = 100 is defined. B ₄₀ and B ₁₀₀ are the ethylene content of EP contained in each fraction, but it is practically impossible to analytically determine these values. The reason is that there is no means for completely separating and separating PP and EP mixed in the fraction. As a result of examination using various model samples, it was found that B ₄₀ can well explain the effect of improving the physical properties of the material by using the ethylene content corresponding to the peak position of the molecular weight distribution curve of fraction 1. It was Further, B ₁₀₀ has crystallinity derived from ethylene chain, and the amount of EP contained in these fractions is E contained in fraction 1.
Due to the two reasons that it is relatively small compared to the amount of P, the approximation of 100 is closer to the actual situation and there is almost no error in calculation. Therefore, B ₁₀₀ = 100 is set for analysis.

(3) The EP content is calculated according to the following formula. EP content _{(wt%) = W 40 × A 40} / B 40 + W 100 × A 100/100 (II) _{ie, W 40 × A 40 / B} 40 is a first term of formula (II) the right side
Indicates the EP content (% by weight) having no crystallinity, and the second term W ₁₀₀ × A _100/100 indicates the EP content (% by weight) having crystallinity. Here, the average ethylene contents A ₄₀ and A ₁₀₀ of the respective fractions 1 and 2 obtained by B ₄₀ and CFC measurement are determined as follows. Figure 2
Is the fraction 1 separated by the difference in crystal distribution.
Of the ethylene content measured corresponding to the curve obtained by measuring the molecular weight distribution with a GPC column constituting a part of the CFC analyzer and the FT-IR connected after the GPC column. It is an example showing a distribution curve. The ethylene content corresponding to the peak position of the molecular weight distribution curve is B ₄₀ . In addition, in FIG. 2, the sum of the products of the weight ratio of each data point and the ethylene content of each data point, which are taken in as data points at the time of measurement, is the average ethylene content A _{40 of the} fraction 1.
Becomes The average ethylene content A _{100 of} fraction 2 is determined in the same manner.

The significance of setting the above three types of separation temperatures is as follows. In the CFC analysis of the present invention,
40 ° C. is a temperature condition necessary and sufficient to separate only polymers having no crystallinity (for example, most of EP, or extremely low molecular weight components and atactic components among propylene polymer components (PP)). It has a certain meaning. 100 ° C. means only a component that is insoluble at 40 ° C. but soluble at 100 ° C. (for example, a component having crystallinity in EP due to the chain of ethylene and / or propylene, and PP having low crystallinity) Is a temperature necessary and sufficient for the elution. 140 ° C. means a component which is insoluble at 100 ° C. but soluble at 140 ° C. (for example, a component having particularly high crystallinity in PP and a component having extremely high molecular weight and extremely high ethylene crystallinity in EP) It is a temperature necessary and sufficient to elute only the total amount of the propylene-based block copolymer used for analysis. Note that W
_{14 0} or not included EP component at all to be excluded from the calculation of the EP content and G since the presence also a very small amount substantially negligible.

<G value> Ethylene content in EP (G) (% by weight) = (W ₄₀ × A
₄₀ + W ₁₀₀ × A ₁₀₀ ) / [EP] Here, [EP] is the EP content (% by weight) previously obtained. <Q value of high crystalline polypropylene component, α, β> Q value,
α and β are obtained from the molecular weight distribution curve of the above-mentioned CFC fraction 3 (a component that is insoluble at 100 ° C. and elutes at 140 ° C.). The method of calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn) from the molecular weight distribution curve of Fraction 3 is a known method, and Mw / Mn is taken as the Q value. α and β are obtained by the following procedure. (1) The common logarithm P of the molecular weight giving the peak of the molecular weight distribution curve of fraction 3 is determined. (2) Obtain the common logarithm of the molecular weight that is 5% higher than the peak height of the molecular weight distribution curve. The molecular weight that gives 5% height is
It exists on both the high molecular weight side and the low molecular weight side across the peak of the molecular weight distribution curve. Of these, the common logarithm of the low molecular weight side is L, and the common logarithm of the high molecular weight side is H. (3) Define α = H-P and β = P-L, and calculate α and β. It is to be noted that FIG. 3 shows an example of a molecular weight distribution chart of fraction 3 and P, L, H and α, β in the example.

Requirement (6) Melting point of propylene block copolymer The propylene block copolymer of the present invention must have a melting point of 157 ° C or higher. Melting point 157 ° C
If it is less than this, heat resistance and rigidity are insufficient. In order to obtain such a propylene-based block copolymer having a high melting point, a metallocene complex, a cocatalyst, polymerization conditions and the like are used in an appropriate combination. Generally, this can often be achieved by increasing the polymerization pressure and / or decreasing the polymerization temperature. It can also be achieved by using the catalyst components (A) to (C) disclosed in the present invention in combination. In the case of a propylene-based block copolymer, the melting point of the product is controlled by the propylene polymer component (PP). Therefore, it can be said that the melting point of the block copolymer is approximately the melting point of PP, and the polymerization reaction in the first step is dominant.

Requirement (7) Content of heterogeneous bond ODC of the propylene block copolymer in the present invention
The B-insoluble component preferably contains a specific amount of different types of bonds (positional irregular units based on 2,1-insertion and 1,3-insertion of propylene). In the present invention, the sum of the 2,1-bond content and the 1,3-bond content is 0.06 to 0.6.
It is preferably mol%. The content of the above bond is ¹³ C
-Measure by NMR.

<Details of ¹³ C-NMR Measurement Method> 1
350 to 500 m in a 0 mmφ sample tube for NMR
The sample of g was added to about 2.0 mL of ODCB and about 0.5 mL of deuterated benzene as a lock solvent in a solvent at 130 ° C.
After completely dissolving with, the measurement is carried out at 130 ° C. by the complete proton decoupling method. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T1 or more (T1 is the longest value of the spin lattice relaxation time of the methyl group) are selected. In the propylene polymer, T1 of the methylene group and the methine group is shorter than that of the methyl group, so that the recovery of the magnetization of all carbons is 99% or more under this measurement condition. From the spectrum measured under the above conditions, the 2,1-bond content and the 1,3-bond content are determined according to the following formulas.

[0033]

[Equation 1]

In this equation, A, A, A, A
, A, A, A, A and A are respectively
42.3 ppm, 35.9 ppm, 38.6 ppm, 3
0.6 ppm, 36.0 ppm, 31.5 ppm, 3
The areas are 1.0 ppm, 37.2 ppm, and 27.4 ppm, and the carbon abundance ratios shown in the following partial structures (I) and (II) are shown.

[0035]

[Chemical 1]

It is not clear why the degree of improvement in impact strength is reduced unless the amount of different bonds is 0.06 mol% or more.
A polymer segment containing a heterogeneous bond has higher mobility than a segment without a heterogeneous bond. Therefore, when a shock is applied, a local plastic deformation can be caused to absorb a larger impact energy. 0.06 mol%
It is presumed that when the ratio is less than, the impact strength is lowered because the effect of generating such a segment having high mobility is small. On the other hand, the heterogeneous bond becomes a defect when the polypropylene forms crystals, and also has the effect of lowering the rigidity. In particular, when it exceeds 0.6 mol%, the crystallinity decreases sharply,
At the same time, the thickness of the crystalline lamella becomes thin, resulting in a decrease in rigidity and heat resistance. The content of these different kinds of bonds can be kept within the range defined by the present invention by selecting an appropriate metallocene complex and combining an appropriate metallocene complex and a cocatalyst. Further, it is possible to keep the polymerization temperature within the range defined by the present invention by carrying out the polymerization at an appropriate polymerization temperature and / or by selecting an appropriate polymerization pressure. As a general fluctuation tendency, when the polymerization temperature is increased, the 1,3-bond content increases, and when the polymerization pressure is increased, the 2,1-bond content increases.

Requirement (8) 1,3-bond content In the propylene block copolymer of the present invention, the 1,3-bond content in the ODCB insoluble component is 0.0.
It is preferably 6 to 0.6 mol%. When the content is 0.06 mol% or more, the mobility of the amorphous component is improved, so that the impact strength improving effect becomes more remarkable. However, when the content exceeds 0.6 mol%, the degree of crystallinity is greatly reduced, resulting in deterioration of rigidity and heat resistance. Among the different types of bonds, the segments containing 1,3-bonds are 2,1-
Due to its higher molecular mobility compared to the segment containing the bond,
It has an excellent effect of improving impact resistance. The content of the 1,3-bond is determined by selecting an appropriate metallocene complex,
The combination of the proper metallocene complex and the co-catalyst can be brought within the scope of the present invention. Further, it is possible to keep the polymerization temperature within the range defined by the present invention by carrying out the polymerization at an appropriate polymerization temperature and / or by selecting an appropriate polymerization pressure.

<Production of Propylene Block Copolymer>
The method for producing a propylene-based block copolymer according to the present invention is not particularly limited as long as it gives a propylene-based block copolymer satisfying the above physical properties,
Among them, a catalyst system suitable for producing the copolymer of the present invention is a specific metallocene catalyst, and an olefin polymerization catalyst obtained by contacting the following components A, B and C as shown below. Can be used

<Component (A)> Transition metal compound component (A)
Is represented by the following general formula (Ia).

[0040]

[Chemical 2]

In the general formula (Ia), R ¹ , R ² , R ⁴ and R
^5's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 12 carbon atoms, or a halogenated hydrocarbon group having 1 to 12 carbon atoms. R
³ and R ⁶ each independently represent a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. R ⁷ and R ⁸ are each independently an aryl group having 6 to 20 carbon atoms and 6 carbon atoms.
~ 20 halogen or halogenated hydrocarbon substituted aryl groups. Q represents a bonding group bridging two conjugated five-membered ring ligands at arbitrary positions, M represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y represent a hydrogen atom or a halogen atom. , A hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. m and n each represent the number of substituents R ⁷ and R ⁸ substituted on the sub ring, and each independently represent an integer of 0 to 20. The transition metal compound of the present invention is preferably a racemate in the case of an object.

The above R ¹ , R ² , R ⁴ , and R ⁵ have 1 to 10 carbon atoms.
Specific examples of the hydrocarbon group of are methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, s
-Butyl, t-butyl, n-pentyl, n-hexyl,
Examples thereof include an alkyl group such as cyclopropyl, cyclopentyl and cyclohexyl, an alkenyl group such as vinyl, propenyl and cyclohexenyl, as well as a phenyl group and a naphthyl group. Specific examples of the silicon-containing hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ , R ² , R ⁴ and R ⁵ include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, bis (trimethylsilyl). ) Examples include alkylsilylalkyl groups such as methyl.

In the above halogenated hydrocarbon group having 1 to 12 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And
When the halogen atom is, for example, a fluorine atom, the above halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, o-,
m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, 2,4
-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, Two
4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like can be mentioned.

Of these, R ¹ and R ⁴ are preferably hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl and phenyl, and R ² and R ⁵ are preferably hydrogen atoms. . As R ³ and R ⁶ , it is preferable that the sub ring formed from the shared portion of the adjacent conjugated five-membered ring is a 7 to 10-membered ring, particularly a pentamethylene group, 1,
A 3-pentadienylene group and a 1,4-pentadienylene group are preferred. Preferable specific examples of the aryl group having 6 to 20 carbon atoms for R ⁷ and R ⁸ include phenyl group, methylphenyl group, dimethylphenyl group, mesityl group, ethylphenyl group, diethylphenyl group, triethylphenyl group,
i-propylphenyl group, di-i-propylphenyl group, tri-i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, Examples of the aryl group include a di-t-butylphenyl group, a tri-t-butylphenyl group, a biphenylyl group, a p-terphenyl group, an m-terphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Of these, t-butylphenyl group, biphenylyl group, p-terphenyl group, naphthyl group, anthryl group and phenanthryl group are particularly preferable.

Examples of the halogen having 6 to 20 carbon atoms or the halogenated hydrocarbon-substituted aryl group of R ⁷ and R ⁸ include the case where halogen is fluorine, chlorine or bromine,
As a specific example, when the halogen atom is, for example, a fluorine atom, a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group can be exemplified. Explaining preferred specific examples by taking fluorine as an example, a fluorophenyl group, a (trifluoromethyl) phenyl group, a methylfluorophenyl group,
Fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro-i-propylphenyl group, fluorodi-i-propylphenyl group, (fluoro-i-propyl ) -I-
Propylphenyl group, fluorotri-i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t-butylfluoro Phenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro-p-terphenyl group, fluoro-m-terphenyl group, fluoronaphthyl group, fluoroanthryl group , A fluorophenanthryl group and the like. The halogenated hydrocarbon group is preferably a fluorinated hydrocarbon-substituted aryl group as the fluorinated compound, and the chlorinated hydrocarbon-substituted aryl group as the chlorinated compound, and is preferably a t-butylfluorophenyl group, a fluorobiphenylyl group, or fluoro-p-terphenyl. Group, fluoronaphthyl group, fluoroanthryl group, fluorophenanthryl group, t-
A butylchlorophenyl group, a chlorobiphenylyl group, a chloro-p-terphenyl group, a chloronaphthyl group, a chloroanthryl group and a chlorophenanthryl group are particularly preferable.

M and n are preferably each independently 1 to
It is an integer of 5. When m and / or n are integers of 2 or more, the plurality of groups R ⁷ (or R ⁸ ) may be the same or different from each other. When m and / or n is 2 or more, R ^{7 s} or R ^{8 s} may be linked to each other to form a new ring structure. The bonding position of R ⁷ and R ⁸ with respect to R ³ and R ⁶ is not particularly limited, but is preferably a carbon adjacent to each 5-membered ring (carbon at α position).

Q is preferably a methylene group, an ethylene group, a silylene group, an oligosilylene group, or a germylene group. M is preferably titanium, zirconium, or hafnium, and particularly preferably hafnium. X and Y are preferably halogen, more preferably chlorine atom. Specific examples of the preferable complex in the component (A) include dimethylsilylenebis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride and dimethylsilylenebis (2-ethyl-4-).
(3-chloro-4-t-butylphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (3-fluoro-4-t-butylphenyl) -4H-azurenyl) hafnium dichloride,
Dimethylsilylene bis (2-ethyl-4-naphthyl-4)
H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4-biphenyl-4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl)
-4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (4-chloro-2-naphthyl-4H-azurenyl)) hafnium dichloride,
Dimethylsilylene bis (2-ethyl-4- (4-chloro-2-tetrahydronaphthyl-4H-tetrahydroazulenyl)) hafnium dichloride, and the like. Among these, dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (4-chloro-2-naphthyl) -4H
-Azulenyl)) hafnium dichloride and dimethylsilylenebis (2-ethyl-4- (3-chloro-4-t-butylphenyl) -4H-azulenyl) hafnium dichloride are preferred.

<Component (B)> In the present invention, as the component (B), a component selected from the group consisting of the following (b-1) to (b-4) is used. (B-1) Particulate carrier carrying aluminum oxy compound, (b-2) Component (A) reacting with component (A)
Particulate carrier carrying an ionic compound or Lewis acid capable of converting cations to cations, (b-3) solid acid particles, (b-4) ion-exchange layered silicate. (B-
Specific examples of the aluminumoxy compound described in 1) include aluminoxane. Also, (b-
Examples of the ionic compound described in 2) include triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (heptafluoro). Naphthyl) borate can be exemplified. As Lewis acid,
Examples thereof include triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, and tris (heptafluoronaphthyl) borane. Examples of the solid acid fine particles (b-3) include magnesium chloride, alumina, and silica alumina. Among these, it is desirable to use (b-4) an ion-exchange layered silicate. In the present invention, the ion-exchange layered silicate used as a raw material (hereinafter simply referred to as silicate) has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and , Refers to a silicate compound in which the contained ions are exchangeable. Since most silicates are naturally produced mainly as the main component of clay minerals, impurities other than ion-exchange layered silicates (quartz, cristobalite, etc.) are often contained, but they are also included. But it's okay. Specific examples of the silicate include the following layered silicates described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995).

That is, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculites such as vermiculite, mica, illite, sericite, mica such as glauconite, attapulgite, Sepiolite, palygorskite, bentonite,
Examples include pyrophyllite, talc, and chlorite groups. In the silicate used as a raw material in the present invention, the main component silicate is 2:
A silicate having a type 1 structure is preferable, a smectite group is more preferable, and montmorillonite is particularly preferable. The type of the interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easily and inexpensively available as an industrial raw material.

(Chemical Treatment) The silicate used in the present invention is
It can be used as it is without any particular treatment, but it is preferably subjected to chemical treatment. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the structure of clay can be used. Specifically, JP-A-5-301917,
JP-A-7-224106, JP-A-8-12761
Known acid treatments, alkali treatments, salt treatments, organic substance treatments and the like disclosed in Japanese Patent Publication No. 3 can be used. Among these treatments, a polymer obtained by treating lithium sulfate and sulfuric acid simultaneously is used to produce a polymer having a higher melting point, higher activity, and a molecular weight distribution of crystalline PP tailed to the polymer side. It is possible to obtain a solid catalyst component which is advantageous for

<Component (C)> Component (C) is an organoaluminum compound, and a compound represented by the general formula AlR ⁹ _P X _3-p is suitable. In this formula, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group or an amino group. p is a number greater than 0 and up to 3. R ⁹ is preferably a trialkylaluminum having 1 to 8 carbon atoms.

(Catalyst Formation / Preliminary Polymerization) The catalyst according to the present invention is formed by bringing the above-mentioned components into contact with each other in a (preliminary) polymerization tank at the same time or continuously, or at once or plural times. be able to.
As these contact methods, various known methods can be used.
Further, the amounts of the components (A), (B) and (C) used in the present invention are arbitrary, and various known methods can be used. The catalyst of the present invention is preferably subjected to a prepolymerization treatment, which comprises contacting it with an olefin and polymerizing it in a small amount. The olefin used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like are used. It can be illustrated. The olefin feed method may be any method such as a feed method of maintaining the olefin in the reaction tank at a constant rate or in a constant pressure state, a combination thereof, or a stepwise change. The temperature and time for prepolymerization are not particularly limited, but each is -20 ° C.
It is preferably in the range of -100 ° C and 5 minutes to 24 hours. The amount of the prepolymerized polymer is preferably 0.01 to 100 g, more preferably 0.1 to 50 g, based on 1 g of the component (B). Further, the component (C) can be added or added during the prepolymerization. A method in which a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania is allowed to coexist during or after the contact of each of the above components is also possible.

[Polymerization / Production of Propylene-Based Block Copolymer] As a method for producing the block copolymer of the present invention, the preceding step of producing the propylene polymer component (PP) is followed by the propylene-ethylene copolymer component. (E
It is composed of the latter step of producing P), and in each step, either the bulk polymerization method or the gas phase polymerization method can be adopted. However, in the latter step, since EP to be produced is a rubber component and it is desirable that it is not eluted in a solvent,
A gas phase polymerization method is preferably adopted. Further, as the polymerization method, either a batch method or a continuous method can be adopted for both the first step and the second step. In the present invention, a two-stage polymerization consisting of a former stage and a latter stage is usually carried out, but in some cases, each stage can be further divided. In particular, a method of making various kinds of rubber components by dividing the latter step into two or more steps is also one of the physical property improving methods.

Method for Producing Propylene Polymer Component (PP) PP is produced in the preceding polymerization step. Homopolymerization of propylene using a metallocene catalyst, preferably a catalyst comprising components (A) to (C) described above, or propylene /
Copolymerization of α-olefin. That is, a propylene homopolymer or a copolymer of propylene and an α-olefin is provided in a single stage or multiple stages in an amount of 50 to 95% by weight, preferably 60 to 92% by weight, based on the total polymerization amount (whole propylene block copolymer). This is a step of forming so as to correspond to. The content of α-olefin in the polymer is 0. 0 based on all monomers (the total of propylene and α-olefin).
It is less than 5% by weight. In the present invention, the α-olefin is a concept of olefin other than propylene including ethylene. Although PP is preferably a propylene homopolymer, ethylene is most preferable as the α-olefin in the case of producing a copolymer with α-olefin.

One of the characteristics of the block copolymer of the present invention is that PP has a high melting point as shown in the requirement (6). In order to produce such a high melting point PP, the metallocene complex is selected, or the polymerization conditions capable of producing the high melting point PP, such as the polymerization temperature, the polymerization pressure, the selection of the cocatalyst, etc., are selected depending on the individual properties of the metallocene complex. Condition selection is required. The conditions to be taken differ depending on the individual complex, but generally higher polymerization pressure is preferred. Generally, the lower the polymerization temperature is, the more preferable it is, but there is a complex having the opposite property, and therefore it cannot be unconditionally specified. In such a case, the preferable conditions are, for example, a polymerization temperature of 30 to 120 ° C, preferably about 50 to 80 ° C. Polymerization pressure is 0.1
It is 5 MPa, preferably 0.1 to 3 MPa. Also,
It is preferable to use a molecular weight regulator so that the fluidity (MFR) of the final polymer is appropriate, and hydrogen is preferable as the molecular weight regulator. Further, the Q value and α / β of the high crystalline polypropylene component determined by the cross fractionation method have a specific relationship, that is, the Q value ≧ 2.3 and α / β ≧ 0.
It is necessary to satisfy the 4 × Q value, which is PP
This can be achieved by polymerizing a specific complex under specific polymerization conditions in the polymerization in the first stage for generating the. As the polymerization method, the type of complex, the type and amount of the organoaluminum compound,
Although the molecular weight is controlled by the polymerization temperature and the amount of hydrogen, it is considered that there are active sites with different chain transfer properties to hydrogen in the catalyst, and the polymerization conditions are adopted so that the difference in the properties of the active sites can be emphasized. This is very important. For example, by suppressing chain transfer other than hydrogen (for example, organoaluminum), chain transfer by hydrogen can be the main component for controlling the molecular weight. For this purpose, it is effective to reduce the amount of the organoaluminum compound to be used or to use an organoaluminum compound having 4 or more carbons which hardly causes chain transfer. Further, as a co-catalyst for activating the metallocene catalyst,
Using a clay mineral treated with a specific salt (for example, a lithium sulfate salt) is also one of the effective methods for obtaining a polymer satisfying the above properties. However, the method is not limited to these.

Propylene-ethylene copolymer component (E
P) Production method In the latter polymerization step of the present invention, an ethylene / propylene copolymer having a weight ratio of propylene and ethylene of 35/65 to 85/15 is produced. In this step, an amount corresponding to 5 to 50% by weight, preferably 8 to 40% by weight of the total amount of polymerization (whole propylene block copolymer) is formed. In this step, an active hydrogen-containing compound or an electron-donating compound such as a nitrogen-containing compound or an oxygen-containing compound may be present.

The propylene block copolymer of the present invention thus obtained may optionally contain an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, After blending various additives such as inorganic or organic fillers, and further various synthetic resins, it is possible to heat-melt and knead using a melt-kneading machine, and then use it as pellets cut into granules as a molding material. is there. These pellet-shaped molding materials are molded by various known polypropylene molding methods, for example, injection molding, extrusion molding, foam molding, blow molding and other techniques, and various industrial injection molded parts, various containers, unstretched films. It is possible to produce various molded products such as uniaxially stretched film, biaxially stretched film, sheet, pipe and fiber. As the physical properties of the molded product, the flexural modulus is 920 MPa or more, preferably 940.
It is possible to easily manufacture a product having a MPa or more and a deflection temperature under load of 109 ° C. or more, preferably 110 ° C. or more.

<Examples> The following examples serve to explain the present invention more specifically. The present invention is not limited by these examples without departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere. The solvent is
What was dehydrated with Molecular Sieve MS-4A was used. Below, the measuring method and apparatus of each physical-property value in this invention are shown.

(1) MFR device Melt indexer measuring method manufactured by Takara Corporation JIS-K7210 (230 ° C, 2.16k)
g load). (2) Content of propylene in the portion insoluble in ODCB at 100 ° C It was determined from the infrared absorption spectrum of the component insoluble in ODCB at 100 ° C, which was recovered according to the method described above. (3) Ethylene content (G) of EP and EP content in the whole propylene block copolymer were measured according to the methods described above. (4) Q value of high crystalline polypropylene component, α / β Measured according to the method described above.

(5) Melting point Using a DSC7 differential scanning calorimeter manufactured by Perkin-Elmer Co., the sample was heated from room temperature to 230 ° C. at 80 ° C./min.
Up to 50 ° C. at −10 ° C./min and held at the same temperature for 3 min.
The peak temperature at the time of melting under the temperature rising condition of 10 ° C./min was defined as the melting point. (6) Flexural modulus (FM) (unit: MPa) Measured at 23 ° C. according to JIS-K7203. The dimensions of the molded product used were 90 × 10 × 4 mm. (7) IZOD impact strength (Unit: kJ
/ M < ² >) It measured at -30 degreeC based on JIS-K7110.

(8) Deflection temperature under load (unit: ° C) According to JIS-K7207, 4.6 kgf / cm ²
It was measured under the conditions. However, in order to adjust the condition of the test piece before measurement, after molding, an operation of annealing at 100 ° C. for 30 minutes and cooling to room temperature is performed. (9) Blend 2 parts of the black pigment masterbatch into the flow mark pellets,
Using an injection molding machine with a mold clamping pressure of 170 tons, a molding temperature of 220
A sheet having a shape of 350 mm × 100 mm × 2 mm was formed at 0 ° C., and the flow mark generation distance was measured and judged. Judgment Criteria ○: Generation distance exceeds 250 mm Δ: Generation distance exceeds 150 mm and 250 mm or less ×: Generation distance is 150 mm or less

Example 1 [Synthesis Synthesis] (1) Dichloro {1,1′-dimethylsilylenebis [2
-Ethyl-4- (2-fluoro-4-biphenyl) -4
Synthesis of H-azulenyl]} hafnium: (a) Synthesis of racemic meso mixture; 2-Fluoro-4-
Bromobiphenyl (4.63 g, 18.5 mmol) was added to diethyl ether (40 mL) and hexane (40 mL).
Was dissolved in the mixed solvent of, and a pentane solution of t-butyllithium (22.8 mL, 36.9 mmol, 1.62 N) was added dropwise at -78 ° C, and the mixture was stirred at -5 ° C for 2 hours. 2-Ethylazulene (2.36 g, 16.6 mmo) was added to this solution.
1) was added and the mixture was stirred at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (40 mL) was added. N-Methylimidazole (40 μL) and dimethyldichlorosilane (1.0 mL, 8.30 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, add dilute hydrochloric acid,
After liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenylyl) -1,4-
A crude product of dihydroazulene (6.3 g) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (23 mL), and n-butyllithium hexane solution (10.3 mL, 16.6 mm) was added at -78 ° C.
ol, 1.56 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours. In addition, toluene (185m
L) was added, the mixture was cooled to −78 ° C., hafnium tetrachloride (2.65 g, 8.3 mmol) was added, the temperature was gradually raised, and the mixture was stirred overnight at room temperature. Most of the solvent was distilled off from the obtained slurry solution under reduced pressure, and after filtration, toluene (4 m
L), hexane (9 mL), ethanol (20 mL),
Wash with hexane (10 mL) and dichloro {1,
1'-Dimethylsilylenebis [2-ethyl-4- (2-
Fluoro-4-biphenylyl) -4H-azulenyl]}
A racemic meso mixture of hafnium (1.22 mg, 16% yield) was obtained.

(B) Purification of racemic compound: The crudely purified product (1.1 g) of the racemic / meso mixture obtained above was suspended in dichloromethane (30 mL) and irradiated with 30 spectra using a high pressure mercury lamp (100 W). .. The solvent of this solution was distilled off under reduced pressure. Dichloromethane (40 mL) was added to the obtained solid to suspend it, and the suspension was filtered. Wash with hexane (3 mL),
When dried under reduced pressure, the racemic purified product (577 mg, 52
%)was gotten. ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.02
(S, 6H, SiMe ₂ ), 1.08 (t, J = 8H
z, 6H, CH ₃ CH ₂ ), 2.54 (sept, J = 8)
Hz, 2H, CH ₃ CH ₂ ), 2.70 (sept, J =
_{8Hz, 2H, CH 3 CH 2} ), 5.07 (brs, 2
H, 4-H), 5.85-6.10 (m, 8H), 6.
83 (d, J = 12 Hz, 2H), 7.30-7.6.
(M, 16H, arom).

[Chemical treatment of ion-exchange layered silicate] 500 g of ion-exchanged water was placed in a 5 L separable flask equipped with a stirring blade and a reflux device, and lithium sulfate 611 was added.
Add g (5.93 mol) and stir. Separately, 581 g (5.93 mol) of sulfuric acid is diluted with 500 g of ion-exchanged water, and the mixture is added dropwise to the lithium sulfate aqueous solution using a dropping funnel. Then, a commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Inc., Benclay SL, average particle size: 28.0)
(350 μm) is added and stirred. Then, the temperature is raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. This slurry was subjected to vacuum filtration with a device in which an aspirator was connected to a nutsche and a suction bottle. The cake was recovered, 5.0 L of pure water was added to re-slurry, and filtration was performed. This operation was repeated 5 more times. The filtration was completed within a few minutes. The pH of the final washing liquid (filtrate) was 5. The collected cake was dried overnight at 110 ° C. under a nitrogen atmosphere. as a result,
290 g of a chemically treated product was obtained. When composition analysis was performed by fluorescent X-ray, the molar ratio of the constituent elements to silicon as the main component was Al / Si = 0.18, Mg / Si = 0.
042 and Fe / Si = 0.020.

[Catalyst Preparation / Preliminary Polymerization]
It was carried out using a solvent and a monomer that had been deoxidized and dehydrated under an inert gas. The chemically treated ion-exchange layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours. 200 g of the chemically treated montmorillonite obtained above was introduced into an autoclave having an internal volume of 10 L, 1160 mL of heptane, and 840 mL (0.5 m) of a heptane solution of triethylaluminum (0.6 mmol / mL).
was added over 30 minutes, and the mixture was stirred at 25 ° C. for 1 hour. The slurry is then allowed to settle and the supernatant 1300
After extracting mL, the mixture was washed twice with 2500 mL of heptane, and heptane was added so that the total amount of heptane finally became 1200 mL. Next, in a 2 L flask, 5.93 g (6 mol) of dimethylsilylene bis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride and 516 m of heptane were added.
After adding L and stirring well, 84 mL of a heptane solution of triisobutylaluminum (140 mg / mL)
(11.8 g) was added at room temperature, and the mixture was stirred for 60 minutes. Then, the above solution was introduced into the montmorillonite slurry prepared in the autoclave previously, stirred for 60 minutes, and heptane was further introduced until the total volume became 5 L, and kept at 30 ° C. Propylene there at a constant speed of 100 g / hr, 4
It was introduced at 0 ° C for 4 hours and then maintained at 50 ° C for 2 hours. The prepolymerized catalyst slurry was collected with a siphon, the supernatant was removed, and then dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 1.7 g of polypropylene per 1 g of the solid catalyst was obtained.

[Polymerization / Production of Propylene Block Copolymer] In a well-dried autoclave equipped with a 3 L stirring blade, 200 mg of triisobutylaluminum and 140 Nm of hydrogen were added.
After introducing L and 750 g of propylene, the temperature in the polymerization tank was kept at 65 ° C., and 55 mg of the prepolymerization catalyst obtained above was pressed in as a solid catalyst component to start bulk polymerization of propylene (preliminary polymerization). Keep the temperature at 65 ° C during the polymerization,
Further, hydrogen was continuously introduced at a rate of 220 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system would be constant. 1
After a lapse of time, unreacted monomers were purged and subsequently replaced with nitrogen gas. Furthermore, propylene and ethylene were continuously introduced so that the mole fraction of ethylene was 60 mol% and the mixed gas was introduced until the total pressure of the polymerization tank was 1.8 MPa, and the gas phase of the propylene-ethylene copolymer component (EP) was increased. Polymerization was started (second-stage polymerization). During the polymerization, the ethylene content should be equal to that of ethylene in EP
By introducing a propylene / ethylene mixed gas having a composition of 5 mol%, the mixed gas composition in the polymerization tank was maintained at 60 mol% in terms of the mole fraction of ethylene. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

IRGANOX was added as a compounding component to the obtained powdery propylene block copolymer.
1010 (manufactured by Ciba Specialty Chemicals)
0.10% by weight, IRGAFOS 168 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, and 0.05% by weight of calcium stearate are mixed, kneaded and granulated by a single-screw extruder, and pelletized propylene. A system block copolymer was obtained. The obtained block copolymer pellet was introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C., and a test piece was molded by injection molding.
The flexural modulus, IZOD impact strength, and deflection temperature under load of the obtained injection-molded piece were measured by the methods described above. Further, the flow mark generation distance was measured according to the method described above. The powders obtained in the following examples were also treated in the same manner, and the physical properties were measured in the same manner.

<Example 2> In the post-stage polymerization for producing the EP of Example 1, the composition of the mixed gas introduced at the start of the polymerization was set to 75 mol% of ethylene, and 55 mol of ethylene was added during the polymerization.
Polymerization was performed in the same manner as in Example 1 except that 1% of a mixed gas was introduced.

Comparative Example 1 (1) Synthesis of Complex (r) -Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride
It was synthesized according to the method described in the literature of tallics, vol. 13, p. 964, (1994). (2) Synthesis of catalyst In a glass reactor equipped with a stirring blade having an internal volume of 0.5 L, W
2.4 g of MAOON SiO ₂ (20.
7 mmol-Al) was added, 50 mL of n-heptane was introduced, and 20.0 mL (0.0) of (r) -dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride solution diluted in toluene in advance.
637 mmol), followed by 4.14 mL of triisobutylaluminum (TIBA) .n-heptane solution.
(3.03 mmol) was added. After reacting at room temperature for 2 hours, propylene was allowed to flow and prepolymerization was carried out.
By this operation, 1 g of polypropylene was added per 1 g of the catalyst.
A prepolymerized catalyst containing 3 g was obtained. [Polymerization] In a well-dried autoclave with a 3 L stirring blade,
Triisobutylaluminum 200mg, Hydrogen 100N
After introducing 750 g of propylene and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 100 mg of the catalyst obtained above was converted into a solid catalyst component to initiate bulk polymerization of propylene. Keep the temperature at 65 ° C during the polymerization, and add 100 NmL of hydrogen so that the hydrogen concentration in the gas phase in the polymerization system becomes constant.
It was continuously introduced at a rate of / hr. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas.
Further, in the EP polymerization, the mixed gas composition introduced at the start of the polymerization was adjusted to 55 mol% of ethylene, and the mixed gas of 45 mol% of ethylene was introduced during the polymerization so that the mixed gas set in the polymerization tank was adjusted to 55 mol% of ethylene.
It was kept at mol%. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 30 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Comparative Example 2> 200 ml of triisobutylaluminum was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing g, 140 NmL of hydrogen, 750 g of propylene, and 5 g of ethylene, the temperature in the polymerization tank was maintained at 65 ° C., and 50 mg of the prepolymerized catalyst obtained in Example 1 was pressed in as a solid catalyst component to carry out bulk polymerization of propylene. Started (first stage polymerization). Keep the temperature at 65 ° C during the polymerization, and add hydrogen to keep the hydrogen concentration in the gas phase in the polymerization system constant.
It was continuously introduced at a rate of 0 NmL / hr. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Subsequently, propylene and ethylene were mixed in such a manner that the ethylene mole fraction became 65 mol%, and the total pressure of the polymerization tank was 1.8 MPa so that the gas phase of the propylene-ethylene copolymer component (EP) was increased. Polymerization was started (second-stage polymerization). During the polymerization, 40 mol% of ethylene should be used so that it has the same composition as ethylene in the EP that is produced.
By introducing a propylene / ethylene mixed gas having a composition, the mixed gas composition in the polymerization tank was maintained at 65 mol% in terms of ethylene mole fraction. Also, the temperature in the tank was 65 during polymerization.
The mixed gas was introduced so that the temperature was kept at 0 ° C. and the total pressure was kept at 1.8 MPa. After 50 minutes, unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

Example 3 In a well-dried autoclave with a 3 L stirring blade, 200 m of triisobutylaluminum was added.
After introducing 90 g of hydrogen, 90 NmL of hydrogen and 750 g of propylene, the internal temperature of the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerization catalyst used in Example 1 in terms of a solid catalyst component was injected to start bulk polymerization of propylene. During the polymerization, the temperature is 65
C., and hydrogen was continuously introduced at a rate of 100 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system was constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 65 mol% and the total pressure of the polymerization tank was 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, a mixed gas having a composition of 45 mol% ethylene was introduced so as to have a composition equal to that of ethylene in the EP produced, so that the composition of the mixed gas in the polymerization tank was maintained at 65 mol% in terms of the mole fraction of ethylene. . Further, the temperature in the tank during the polymerization was kept at 65 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 20 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Comparative Example 3> 200 ml of triisobutylaluminum was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing 750 g of propylene and 750 g of propylene, the internal temperature of the polymerization tank was maintained at 65 ° C., and 100 mg of the prepolymerization catalyst used in Comparative Example 1 was pressed in as a solid catalyst component to start bulk polymerization of propylene. The temperature was kept at 65 ° C during the polymerization. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Furthermore, in the subsequent EP polymerization, the mixed gas composition introduced at the start of the polymerization was ethylene 55 mol%
By introducing a mixed gas of 45 mol% ethylene during the polymerization, the mixed gas composition in the polymerization tank was maintained at 55 mol% in terms of the mole fraction of ethylene. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 20 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Example 4> 200 ml of triisobutylaluminum was added to a well-dried autoclave equipped with a 3 L stirring blade.
After introducing g, 300 NmL of hydrogen, and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerization catalyst used in Example 1 in terms of a solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature is 65
The temperature was kept at 0 ° C., and hydrogen was continuously introduced at a rate of 300 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system became constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the ethylene mole fraction became 55 mol%, and the total pressure of the polymerization tank reached 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, a mixed gas composition of ethylene of 30 mol% was introduced so as to be equal to the composition of ethylene in the produced EP, so that the mixed gas composition in the polymerization tank was maintained at 55 mol% in terms of the mole fraction of ethylene. . Further, the temperature in the tank during the polymerization was kept at 65 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 60 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered.

Comparative Example 4 Triisobutylaluminum (200 m) was placed in a well-dried autoclave equipped with a 3 L stirring blade.
g, 200 NmL of hydrogen, and 750 g of propylene were introduced, the temperature in the polymerization tank was kept at 65 ° C., and 100 mg of the prepolymerized catalyst used in Comparative Example 1 was pressed in as a solid catalyst component.
Bulk polymerization of propylene was initiated. Temperature is 6 during polymerization
Hydrogen was continuously introduced at a rate of 150 NmL / hr so that the temperature was kept at 5 ° C. and the hydrogen concentration in the polymerization system was kept constant. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Further, in the EP polymerization, the mixed gas composition introduced at the start of the polymerization was changed to ethylene 40
The composition of the mixed gas in the polymerization tank was kept at 40 mol% in terms of the molar fraction of ethylene by introducing a mixed gas of 30 mol% of ethylene during the polymerization. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 60 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered.

[0076] As shown in <Embodiment 5> FIG. 4, during the stirred gas-phase polymerization vessel 7 equipped with a stirrer liquid phase polymerization vessel 1,0.5M ³ having an inner volume of 0.4 m ^3, sedimentation liquid Power classifier 3, concentrator 4
(Hydrocyclone), a classification system consisting of a counter-current pump 5 and a process incorporating a degassing tank 6 were used to continuously produce a propylene / ethylene block copolymer. Liquefied propylene, hydrogen and triisobutylaluminum (TIBA) were continuously fed to the liquid phase polymerization tank 1. The feed amounts of liquefied propylene and TIBA were 90 kg / hr and 10.6 g / hr, respectively.
and the hydrogen has a molar concentration [H ₂ ] of 270 ppm.
Was fed. Furthermore, the same prepolymerized catalyst as used in Example 1 was used as the solid catalyst component in 2.2.
It was fed so as to be 1 g / hr. Further, the polymerization tank 1 was cooled so that the polymerization temperature was 65 ° C.

The slurry polymerized in the polymerization tank 1 was extracted into the degassing tank 6 through the classification system at a rate of about 17.5 kg / hr as polypropylene particles contained in the slurry. The average residence time of the polypropylene particles in the liquid phase polymerization tank 1 and the circulation line was 1.25 hours. The average particle diameter Dp ₅₀ of the polypropylene particles is 5
55 μm, catalyst efficiency CE 7600 g / g, MFR 5
It was 5.0 g / 10 minutes. The catalyst efficiency CE is defined by the polypropylene yield (g) per 1 g of the solid component contained in the solid catalyst component (A).

In the degassing tank 6, while the propylene gas heated from the lower part is being fed, the temperature inside the tank is 65 ° C.
Maintained at. The solid polypropylene particles obtained here were sent to the gas phase polymerization tank 11 to carry out copolymerization (EPR polymerization) of propylene and ethylene. Polymerization was carried out by controlling so that the sum of the partial pressures of ethylene and propylene was 1.4 MPaG, the mole fraction of ethylene was 60 mol%, and the hydrogen concentration was constant at 30 ppm. Further, ethanol was fed as an active hydrogen compound. The feed amount of ethanol was adjusted to be 0.46 in terms of molar ratio with respect to aluminum in TIBA supplied together with the polymer particles supplied to the gas phase polymerization tank 7. Polymerization temperature is 6
At 5 ° C, the extraction rate of the propylene / ethylene block copolymer extracted from the gas phase polymerization tank 7 is about 20 kg.
It was adjusted to be / hr. The average residence time in the gas phase polymerization tank 7 was 1.5 hours.

When the polymer particles extracted from the gas phase polymerization tank 7 were analyzed, MFR was 32.0 g / 10 min, bulk density (BD) was 0.486 g / cc, and EP content was 1
It was 5.9% by weight. The catalyst efficiency CE of the propylene / ethylene block copolymer was 8600 g / g. IRGANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, IRGAFOS
168 (manufactured by Ciba Specialty Chemicals) 0.
10% by weight of calcium stearate and 0.05% by weight of calcium stearate were mixed, and the mixture was kneaded and granulated with a single-screw extruder to obtain a pellet-shaped resin block copolymer. The block copolymer pellets obtained were introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C.,
A test piece was molded by injection molding. The flexural modulus, IZOD impact strength, and deflection temperature under load of the obtained injection-molded piece were measured by the methods described above. Further, the flow mark generation distance was measured according to the method described above.

Example 6 In Example 5, ethylene was fed so that the mole fraction of ethylene in the gas phase polymerization tank 11 was constant at 70 mol%, and the feed amount of ethanol as an active hydrogen compound was changed to the gas phase. The molar ratio was set to 0.10 with respect to the aluminum in TIBA supplied together with the polymer particles supplied to the polymerization tank 11. When the withdrawal rate of the propylene / ethylene block copolymer withdrawn from the gas phase polymerization tank 11 was adjusted to be about 20 kg / hr, the average residence time in the gas phase polymerization tank 11 was 2.3 hours. When the polymer particles extracted from the gas phase polymerization tank 11 were analyzed, the MFR was 2
5.0 g / 10 minutes, bulk density (BD) 0.483 g /
The cc and EP contents were 17.5% by weight. The catalyst efficiency CE of the propylene / ethylene block copolymer
Was 9500 g / g.

Example 7 A well-dried autoclave equipped with a 3 L stirring blade was charged with 200 m of triisobutylaluminum.
After introducing 50 g of hydrogen, 150 NmL of hydrogen and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 55 mg of the catalyst used in Example 1 in terms of a solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature was kept at 65 ° C., and hydrogen was continuously introduced at a rate of 250 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system became constant. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Furthermore, subsequently, a mixed gas of propylene and ethylene was introduced so that the ethylene mole fraction became 85 mol%, and the total pressure of the polymerization tank reached 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, a mixed gas having a composition of 80 mol% of ethylene was introduced so as to have the same composition of ethylene as that in the EP produced, so that the composition of the mixed gas in the polymerization tank was maintained at 85 mol% in terms of the mole fraction of ethylene. . The temperature in the tank during polymerization is 6
The mixed gas was introduced so as to maintain the temperature at 5 ° C. and the total pressure at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Comparative Example 5> Triisobutylaluminum (200 m) was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing 100 g of hydrogen, 100 NmL of hydrogen and 750 g of propylene, the temperature in the polymerization tank was kept at 65 ° C., and 100 mg of the catalyst used in Comparative Example 1 was pressed in as a solid catalyst component to start bulk polymerization of propylene. During the polymerization, the temperature was kept at 65 ° C., and hydrogen was continuously introduced at a rate of 100 NmL / hr so that the hydrogen concentration in the polymerization system would be constant. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Further, in the subsequent EP polymerization, the mixed gas composition introduced at the start of the polymerization was ethylene 80 mol%.
By introducing a mixed gas of 70 mol% of ethylene during the polymerization, the mixed gas composition in the polymerization tank was maintained at 80 mol% in terms of the mole fraction of ethylene. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

Comparative Example 6 Mg (OE) was placed in a 3 L-round bottom four-necked flask equipped with a vacuum stirrer and a thermometer.
t) ₂ : 2.0 mol was charged, and then Ti (OBu) ₄
Was charged so that Ti (OBu) ₄ /Mg=0.6 (molar ratio) to magnesium in the charged Mg (OEt) ₂ , and the temperature was raised while stirring at 200 rpm.
After reacting at 150 ° C. for 2.0 hours, the temperature was lowered to 120 ° C., and a toluene solution of Si (OPh) ₄ was charged into Mg.
For magnesium in (OEt) ₂ , Si (OP
h) It was added so that _{4 /} Mg = 0.5 (molar ratio). After the addition was completed, the reaction was carried out at the same temperature for 1.0 hour. After the reaction was completed, the temperature was lowered to room temperature, and Si (OEt) ₄ was added to Mg in the charged Mg (OEt) _{2 to} obtain Si.
(OEt) ₄ / Mg was added in an amount of 0.2 (molar ratio) to obtain a slurry of Ti / Mg contact product.

The entire amount of the slurry obtained here is cooled and cooled.
Induction stirring type 10L-autoc with heating jacket
[Mg] = 0.486 mol / L after transfer to the reeve
Diluted with toluene to give toluene. This
Cool the rally to -10 ° C with stirring at 300 rpm.
However, Mg (OEt) charged with diethyl phthalate ₂
Diethyl phthalate / Mg =
0.1 (molar ratio) was added. Continue to T
iCl_FourWas charged with Mg (OEt)₂Magnesium inside
Against TiCl_Four/Mg=4.0 (molar ratio)
Thus, the solution was added dropwise over 1.0 hour to obtain a uniform solution. This
At the time of, the phenomenon that the viscosity of the liquid rises and becomes a gel,
It didn't happen.

The obtained homogeneous solution was heated at 15 ° C. at 0.5 ° C./minute.
The temperature was raised to and held at the same temperature for 1 hour. Then, the temperature was again raised to 50 ° C. at 0.5 ° C./minute, and the temperature was maintained at 50 ° C. for 1 hour. Furthermore, the temperature was raised to 117 ° C. at 1.0 ° C./minute, and the treatment was performed at the same temperature for 1 hour. After completion of the treatment, heating / stirring was stopped, the supernatant liquid was removed, and the residual liquid ratio =
It was washed so as to be 1/50 to obtain a solid slurry. Next, the amount of toluene in the obtained solid slurry is changed to TiCl ₄
The concentration was adjusted to 2.0 mol / L · toluene, and Mg (OE) was initially charged with TiCl ₄ at room temperature.
t) ₂ with respect to magnesium in TiCl ₄ / Mg =
It was added so as to be 5.0 (molar ratio). The temperature of this slurry was raised with stirring at 300 rpm, and at 117 ° C.,
The reaction was carried out for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant liquid was removed, and the residue was washed with toluene so that the residual liquid ratio was 1/150 to obtain a toluene / slurry product of the Ti / Mg contact product. It was The total amount of the solid slurry obtained here,
It is transferred to a reaction tank having an inner diameter of 660 mm and a straight body portion of 770 mm and having three-way retreating blades, diluted with n-hexane, and Ti · M.
The concentration of the g-contact product was set to 3 g / L.
While stirring this slurry at 300 rpm,
Then, triethylaluminum was added so that triethylaluminum / Ti.Mg contact product = 3.44 mmol / g, and t-butylethyldimethoxysilane was added to t-butylethyldimethoxysilane / Ti.
-Mg contact product = 1.44 mmol / g was added. After the addition is complete, continue stirring at 25 ° C.
Held for 30 minutes.

Then, propylene gas was fed into the liquid phase at a constant rate for 72 minutes. After the propylene gas feed was stopped, washing with n-hexane was performed by a sedimentation washing method to obtain a slurry of the solid catalyst component (A) with the residual liquid ratio = 1/12. The obtained prepolymerized catalyst contained 2.7 g of propylene polymer per 1 g of Ti / Mg contact product. In a well-dried autoclave with a 3 L stirring blade, 550 mg of triethylaluminum and 3000 of hydrogen were added.
After introducing NmL and 750 g of propylene, the temperature in the polymerization tank was maintained at 70 ° C., and 10 mg of the solid catalyst component obtained above was pressed in to initiate bulk polymerization of propylene. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 40 mol%, and the total pressure of the polymerization tank was 1.8 MPa.
Gas phase polymerization of P was initiated. The temperature inside the polymerization tank was kept at 75 ° C., and ethylene and propylene were introduced so that the mixed gas composition inside the polymerization tank was kept at 40 mol% in terms of the mole fraction of ethylene. After 45 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered.

<Example 8> [Complex synthesis] Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (3-chloro-4-t-butyl-phenyl)-
Synthesis of 4H-azurenyl]} hafnium: (a) Synthesis of racemic meso mixture; 3-chloro-4-t
-Butyl bromobenzene (4.58g, 18.5mmo
l) diethyl ether (40 mL) and hexane (40
mL) in a mixed solvent of t-butyllithium (22.8 mL, 36.9 mmol, 1.62).
N) was added dropwise at -78 ° C, and the mixture was stirred at -5 ° C for 2 hours. 2-Ethylazulene (2.36 g, 16.6 m) was added to this solution.
(mol) and stirred at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (40 mL) was added. N-Methylimidazole (40 μL) and dimethyldichlorosilane (1.0 mL, 8.30 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, add dilute hydrochloric acid,
After liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (3-chloro-4-t-butylphenyl) -1,
A crude product of 4-dihydroazulene) (6.1 g) was obtained. Next, the crude product obtained above was dissolved in diethyl ether (23 mL), and a solution of n-butyllithium in hexane (10.3 mL, 16.6 mmol, at -78 ° C) was obtained.
1.56 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours. Further, toluene (185 mL) was added, the mixture was cooled to -78 ° C, and hafnium tetrachloride (2.65) was added.
g, 8.3 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. Most of the solvent was distilled off from the resulting slurry solution under reduced pressure, and after filtration, washing with toluene (4 mL), hexane (9 mL), ethanol (20 mL), and hexane (10 mL) resulted in dichloro {1,1 '. -Dimethylsilylenebis [2-ethyl-4- (3-chloro-4)
-T-Butylphenyl) -4H-azurenyl]} hafnium racemic meso mixture (1.70 g, 20% yield)
was gotten.

(B) Purification of racemate: 1.5 g of the obtained mixture was dissolved in 75 mL of dichloromethane and irradiated with 30 spectra by using a high pressure mercury lamp (100 w). The solvent was distilled off from this solution under reduced pressure, washing with hexane was repeated, washing with ether was performed, and drying was performed.
0.27 g of racemic (4-t-butyl-3-chlorophenylyl) -4H-azulenyl]} hafnium was obtained. ¹ H-NMR (CDCl ₃ ) δ 1.00 (s, 6H, Si
Me ₂ ), 1.05 (t, J = 5.6 Hz, 6H, 2-
CH ₂ CH ₃ ), 1.47 (s, 18H, tBu), 2.
4-2.5 (m, 2H, 2- CH 2 CH 3), 2.6-
2.7 (m, 2H, 2- CH 2 CH 3), 4.99 (d,
J = 3.0 Hz, 2H, 4-H), 5.8-6.1.
(M, 6H), 6.78 (d, J = 11.7Hz, 2
H), 7.2-7.6 (m, 12H)

[Chemical treatment of ion-exchange layered silicate] 500 g of ion-exchanged water was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and further 249 g (5.93 mol) of lithium hydroxide monohydrate. Was charged and stirred. Separately, 581 g (5.93 mol) of sulfuric acid was diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. Next, 350 g of commercially available granulated montmorillonite (Ben clay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm) is added, and the mixture is stirred. Then, the temperature is raised to 108 ° C. over 30 minutes and heat treatment is performed for 150 minutes. After the treatment, it was cooled to 50 ° C. over 1 hour. This slurry was subjected to vacuum filtration with a device in which an aspirator was connected to a nutsche and a suction bottle. The cake was recovered, 5.0 L of pure water was added to re-slurry, and filtration was performed. This operation was repeated 4 more times. The filtration was completed within a few minutes. P of the final washing solution (filtrate)
H was 5. Collected cake under nitrogen atmosphere 11
Dry overnight at 0 ° C. As a result, 275 g of a chemically treated product was obtained. When the compositional analysis was performed by fluorescent X-ray, the molar ratio of the constituent elements to the main component, silicon, was found to be Al / S.
i = 0.21, Mg / Si = 0.046, Fe / Si =
It was 0.022.

[Preparation of Catalyst / Preliminary Polymerization]
It was carried out using a solvent and a monomer that had been deoxidized and dehydrated under an inert gas. The chemically treated ion-exchange layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours. 10 g of the chemically treated montmorillonite obtained above was introduced into a round-bottomed flask having an internal volume of 1 L, and heptane 450 was added.
mL, and further heptane solution of triethylaluminum (0.6 mmol / mL) 42 mL (0.025 mo
1) was added over 30 minutes, and the mixture was stirred at 25 ° C for 1 hour.
Then, the slurry was allowed to stand still, 400 mL of the supernatant was withdrawn, then washed twice with 500 mL of heptane, and finally heptane was extracted and adjusted so that the total amount of heptane was 100 mL. Next, dichloro {1,1'-methylsilylene bis [2-ethyl-4- (3-chloro-4-
t-butylphenyl) -4H-azurenyl]} hafnium 0.25 g (0.3 mmol) and heptane 516 mL
, And after stirring well, 84 mL of a heptane solution of triisobutylaluminum (140 mg / mL)
(11.8 g) was added at room temperature, and the mixture was stirred for 60 minutes. Then, the above solution was introduced into the montmorillonite slurry prepared in the autoclave previously, stirred for 60 minutes, and heptane was further introduced until the total volume became 5 L, and kept at 30 ° C. Propylene there at a constant speed of 100 g / hr, 4
It was introduced at 0 ° C for 4 hours and then maintained at 50 ° C for 2 hours. The prepolymerized catalyst slurry was collected with a siphon, the supernatant was removed, and then dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization] Polymerization was carried out in the same manner as in Example 1 except that 55 mg of the above prepolymerized catalyst was used as the solid catalyst component.

IRGANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight of IRGANOX1010 and IRGANOX1010
FOS168 (Ciba Specialty Chemicals) 0.10% by weight, calcium stearate 0.05
The mixture was blended at a blending ratio (wt%) of wt%, and kneaded and granulated with a single-screw extruder to obtain a pellet-shaped resin block copolymer. The block copolymer pellets obtained were molded at a mold temperature of 40.
The test piece was introduced into an injection molding machine heated at 0 ° C. and a cylinder temperature of 220 ° C., and a test piece was molded by injection molding. With respect to the obtained injection-molded piece, flexural modulus, IZO were measured by the method described above.
D impact strength and deflection temperature under load were measured. Further, the flow mark generation distance was measured according to the method described above.

The results of Examples and Comparative Examples are summarized in Table 1 (No. 1), Table 1 (No. 2) and Table 3 (No. 3).
In the table, "nd" means undetectable.

[0095]

[Table 1] Table 1 (1)

[0096]

[Table 2] Table 1 (Part 2)

[0097]

[Table 3] Table 1 (Part 3)

[0098]

EFFECTS OF THE INVENTION When the propylene block copolymer of the present invention is used as a molding material, it exhibits a very good balance of rigidity-impact resistance, good heat resistance and excellent moldability. It has a good appearance.

[Brief description of drawings]

FIG. 1 is a conceptual flow chart of CFC-FT-IR.

FIG. 2 is a GPC-FT-IR analysis result diagram of fraction 1.

FIG. 3 is a diagram showing the molecular weight distribution of Fraction 3 and P, L, H and α, β.

FIG. 4 is a manufacturing process flow chart of the continuous two-stage polymerization method.

[Explanation of symbols]

1. Liquid phase polymerization tank 2. Slurry circulation pump 3. Sedimentation liquid force classifier 4. Concentrator (hydrocyclone) 5. Countercurrent pump 6. Degassing tank 7. Gas phase polymerization tank

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaaki Ito             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Co., Ltd. Catalyst Development Center (72) Inventor Yu Hayakawa             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Material Development Center F-term (reference) 4J026 HA04 HA27 HA35 HB03 HB04                       HB27 HB35 HB43 HB48 HE02

Claims (3)

[Claims] 1. A propylene-based block copolymer obtained by a first step of producing a propylene polymer component (PP) and a second step of producing a propylene-ethylene copolymer component (EP) using a metallocene catalyst. And the said block copolymer satisfies the following requirements (1)-(6), The propylene type block copolymer characterized by the above-mentioned. (1) Melt flow rate (MFR) is 0.1 to 15
It is 0 g / 10 minutes. (2) The propylene content of the component which is insoluble in ortho-dichlorobenzene at 100 ° C and soluble in ortho-dichlorobenzene at 140 ° C is 99.5% by weight or more. (3) Propylene in propylene block copolymer
The content of the ethylene copolymer component (EP) is 5 to 50% by weight. (4) The ethylene content (G) of EP is 15 to 65% by weight. (5) Mw / M, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the highly crystalline polypropylene component in the propylene block copolymer, which is determined by the cross fractionation method.
Let n be the Q value, and P be the common logarithm of the molecular weight corresponding to the peak position of the molecular weight distribution curve of the high crystalline polypropylene component, and L and H (L is Lower molecular weight than peak molecular weight, H
Is higher than the peak molecular weight), and α and β are defined as α = HP and β = P−L, respectively, the Q value and α / β satisfy the following relationship. A) Q value ≧ 2.3 a) α / β ≧ 0.4 × Q value (6) The melting point of the block copolymer is 157 ° C. or higher. 2. The sum of the 2,1-bond content and the 1,3-bond content in the component insoluble in ortho-dichlorobenzene at 100 ° C. and soluble in ortho-dichlorobenzene at 140 ° C. is 0. The propylene-based block copolymer according to claim 1, which is from 0.06 to 0.6 mol%. 3. The content of 1,3-bonds in the component insoluble in ortho-dichlorobenzene at 100 ° C. and soluble in ortho-dichlorobenzene at 140 ° C. is 0.06 to 0.6 mol%. Item 1. The propylene block copolymer according to Item 1.