JP2003147157A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition which is excellent in mechanical strengths (particularly, rigidity, low-temperature impact resistance and heat resistance), is industrially useful as a fabricated material for injection molding or extrusion, and can be used automobile parts of thin thickness and light weight so that it can contribute to the saving of energy and resources. SOLUTION: This polypropylene resin composition contains (a) 10-99 wt.% of a propylene block copolymer obtained by using a metallocene catalyst through the former step of producing a propylene polymer component (PP) and the latter step of producing a propylene/ethylene copolymer component (EP) and having specified physical properties, and (b) 1-90 wt.% of an elastomer. In addition, (c) a polypropylene resin produced by using a Ziegler catalyst can also be blended with the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel propylene resin composition. More specifically, the present invention relates to a propylene resin composition having excellent balance of rigidity, impact resistance (particularly low temperature impact resistance) and heat resistance, which is useful as a material for injection molding, extrusion molding or blow molding. .

[0002]

2. Description of the Related Art Polypropylene has hitherto been widely used as a molding material for injection molded products, extrusion molded products, hollow molded products and the like. In recent years, from the viewpoint of resource saving and energy saving, it has been required to reduce the thickness and weight of molded products such as injection molded products. By improving the balance between rigidity and impact resistance of polypropylene molding materials, molding products can be improved. Various proposals have been made to enable thinning and weight reduction of the.

For example, it is known to use a block copolymer produced by stepwise polymerizing propylene and ethylene or another olefin to achieve thinning and weight reduction. Further, recently, a propylene block copolymer polymerized in the presence of a catalyst system consisting of a metallocene compound and a cocatalyst has been proposed as a polypropylene having improved physical properties such as low temperature impact resistance (Japanese Patent Laid-Open No. 4-337308). Japanese Patent Laid-Open No. 5-202152, Japanese Patent Laid-Open No. 6-206
No. 921, Special Publication No. 8-510491, WO9
5/27740, WO95 / 27741, etc.). The present inventor has also proposed an improved method for the above catalyst system using a specific carrier and a specific polymerization method (Japanese Patent Laid-Open No. 6-58242).
-172414, JP-A-6-287257, and JP-A-8-27237).

However, the polypropylene obtained by these methods does not always have a sufficient balance between rigidity, impact strength (particularly low temperature impact strength) and heat resistance, and further improvement is required.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a propylene resin composition capable of easily producing a molded article having an excellent balance of rigidity, impact resistance (particularly low temperature impact resistance) and heat resistance. Is an issue.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a propylene-based block copolymer produced with a metallocene catalyst, and as a result, have found that the propylene polymer component (P
By using a propylene-based block polymer containing P) and an ethylene-propylene copolymer component (EP) having a specific structure in a specific ratio and combining this with an elastomer, rigidity and impact resistance (especially at low temperature) can be obtained. The inventors have found that a molded product having an excellent balance between impact resistance) and heat resistance can be obtained, and have reached the present invention.

That is, according to the present invention, (a) the preceding step of producing the propylene polymer component (PP) using the metallocene catalyst and the propylene-ethylene copolymer component (E)
P), which is obtained by a subsequent step and contains 10 to 99% by weight of a propylene-based block copolymer satisfying the following requirements (1) to (6), and (b) an elastomer of 1 to 90% by weight. A characteristic propylene-based resin composition (hereinafter referred to as "composition I") is provided. (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 10 to 90% by weight. (5) The relational expression (I) is established between the ethylene content (G) of EP and the ethylene content (E) of a component having no crystallinity in EP. G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G − 7.0 (I) (6) The melting point of the block copolymer is 157 ° C. or higher.

Further, the present invention is obtained by (a) using a metallocene catalyst, a pre-process for producing a propylene polymer component (PP) and a post-process for producing a propylene-ethylene copolymer component (EP), Requirements (1) above
Propylene block copolymers 10 to 9 satisfying (6)
4% by weight, (b) 1 to 85% by weight of an elastomer, and (c) 5 to 60% by weight of a polypropylene resin produced by using a Ziegler type catalyst. "Composition II".)
Is provided.

Further, the present invention is a molded article selected from the group consisting of injection molded articles, injection compression molded articles, hollow molded articles, and extrusion molded articles, wherein the above-mentioned "composition I" or "composition I" is used.
The present invention provides a propylene-based resin molded product characterized by being composed of "I".

The propylene-based resin composition of the present invention is obtained by blending a specific propylene-based block copolymer with an elastomer and, if necessary, a polypropylene resin obtained by using a Ziegler-based catalyst. By using a block polymer having a specific structure produced by using a metallocene catalyst as a block polymer, a molding material having an excellent balance of rigidity, impact resistance (particularly low temperature impact resistance) and heat resistance can be obtained. Is what you can get.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The propylene-based resin composition of the present invention comprises a propylene-based block copolymer and a blending component for the propylene-based block copolymer.

(I) Description of Propylene-Based Block Copolymer The (a) propylene-based block copolymer of the present invention comprises a metallocene catalyst-based pre-process for producing a propylene polymer component (PP) and propylene-ethylene. It is obtained by the latter step of producing the copolymer component (EP) and 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 10 to 90% by weight. (5) The relational expression (I) is established between the ethylene content (G) of EP and the ethylene content (E) of a component having no crystallinity in EP. G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G − 7.0 (I) (6) The melting point of the block copolymer is 157 ° C. or higher.

(Ii) Description of Requirements (1) to (6) (1) Melt Flow Rate (MFR) The propylene block copolymer of the present invention has an MFR in the range of 0.1 to 150 g / 10 minutes. It is necessary to be. 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. 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 0.5% by weight or less of α-olefin in the raw material gas composition. The insoluble component is
It refers to a component that is obtained by using a known temperature rising column fractionation method and is insoluble in ODCB at 100 ° C. but soluble in ODCB at 140 ° C. The heating column fractionation method is, for example, Macromolec
ules, 21, 314-319 (1988).

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, while maintaining the column temperature 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 ".

ODCB is a good solvent for polyolefins and has a high boiling point of 181 ° C., so that 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, particularly 55 to 90% by weight.

Requirement (3) Propylene block copolymer
EP content in the propylene-based block copolymer of the present invention, the weight ratio of the propylene-ethylene copolymer component in it,
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.
Generally, in a propylene-based block copolymer, the propylene-ethylene copolymer is a random copolymer, and a substance having poor crystallinity and exhibiting physical properties such as rubber is a main component, and it is a basic component that develops impact strength. Become a factor. In the present invention, since the propylene-ethylene copolymer has high random copolymerizability, the EP content is 5 to 50% by weight.
It exhibits excellent physical properties in a wide range. If the EP content is less than 5% by weight, the rubber-like portion is too small and the impact strength deteriorates. On the contrary, if the EP content is 50% by weight or more,
There is a problem that the rigidity is lowered due to too few crystalline parts. In the present invention, the preferred EP content is 10 to 10.
It is in the range of 40% by weight, particularly preferably 10 to 30% by weight. The definition and measurement method of the EP content in the propylene block copolymer which is the subject of the present invention 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 10 to 90% by weight. It is preferably 20 to 60% by weight, more preferably 25 to 50% 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 10% by weight,
As a result of the increase in the glass transition temperature of EP, there is the disadvantage that the impact strength at low temperatures decreases. Further, a phenomenon occurs in which a part of EP is solubilized in PP serving as a matrix, which causes a problem that rigidity and heat resistance are lowered. On the other hand, when G exceeds 90% by weight, EP is not uniformly dispersed in PP and impact strength is reduced. 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) Relationship between G and E In the propylene block copolymer of the present invention, the ethylene content (G) of EP and the ethylene content (E) of the non-crystalline component of EP are In between, the following relational expression (I)
It is necessary that G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G −7.0 (I)

EP is a propylene-ethylene random copolymer, which is mainly composed of rubber-like molecules having no crystallinity, but has a portion having crystallinity based on a relatively long ethylene chain and / or propylene chain. Molecules may also be present. The impact absorption characteristics of the propylene-based block copolymer strongly depend on the glass transition temperature of the rubber portion, and the E value is an index showing the high glass transition temperature. Further, the E value also serves as an index showing the affinity between the PP phase and the EP phase, and the dispersed particle size of EP is strongly influenced by the E value. On the other hand, the G value is an index of the average ethylene content of all EPs including molecules having crystallinity and molecules having no crystallinity. The G value and the E value generally show a positive correlation, and the higher the G value, the higher the E.

That is, the higher the average ethylene content of all EPs, the higher the ethylene content of the rubber component having no crystallinity. The G value is always larger than the E value. The magnitude relationship does not reverse, and the theoretical limit is G = E. The propylene block copolymer has a form in which the EP component is spherically dispersed in the polypropylene continuous phase, and when the inside of the spherical EP dispersed phase is observed more microscopically, the rubber part (rubber component )
It is general that lamellae derived from a crystalline component are mixed.

As a result of repeated examinations of various physical properties of EP, the inventors of the present invention should not increase the difference between the G value and the E value, that is, make a straight line of E = G in which the theoretical upper limit of the E value is plotted. It has been found that bringing them closer to each other leads to improvement in physical properties, which is the subject of the present invention. The propylene-based block copolymer disclosed in the present invention has a very high randomness of EP, so that the physical property correlation between the G value and the E value has a theoretical upper limit line as compared with conventionally known block copolymers. The physical properties are closer to E = G shown. Further, in the present invention, 10 ≦ G ≦ 90, preferably 20
Since ≦ G ≦ 60, and more preferably 25 ≦ G ≦ 50, the propylene-based block copolymer of the present subject matter has E
-G belongs to a region that satisfies a certain condition. In other words, the difference between the G value and the E value is usually within 5% by weight, preferably within 3% by weight, and particularly 2% by weight.
Within. Especially when the G value is in the range of 20 to 50% by weight,
The difference between the E value and the E value is 0 to 2% by weight, more preferably 0 to 1% by weight.

When the G value and the E value do not satisfy the relational expression (I), the strength of the affinity between the amorphous component and the crystalline component in EP does not reach the critical point, so that the impact resistance is high. It is speculated that the balance between flexibility and rigidity will not be improved to a satisfactory level. Further, when the relationship between the G value and the E value does not satisfy the above relational expression (I), PP which is a crystal part and E which is a rubber part.
As a result of the higher affinity of P, the particle size of EP particles dispersed in the PP phase becomes smaller, the gloss increases, and a good appearance cannot be obtained. The reason for the deterioration of the physical properties, particularly the balance between rigidity and impact resistance, is that the same EP is caused by the fact that the size of lamellae present in rubber increases or agglomerates.
It is considered that the impact absorption capacity changes even when the content is increased. Further, the size of the dispersed EP particles also changes at the same time, resulting in an inconvenience that the gloss value increases. On the contrary, as the G value and the E value approach, the lamella dispersed in the rubber becomes smaller, and the degree of cohesion decreases, so it is possible to maintain a good rigidity / impact resistance balance with a low gloss value. It is believed that
The G value can be set to a desired value by changing the ethylene / propylene raw material composition ratio in the latter step. Further, the E value can satisfy the relational expression (I) of the requirement (5) of the present invention by appropriately selecting the catalyst and the polymerization condition as described later.

< Determination of Parameters of Requirements (3) to (5)
Method> In the present invention, the EP content in the propylene-based block copolymer, the ethylene content (G) in the EP and E
The ethylene content (E) of the portion having no crystallinity in P is 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) After the CFC, a GPC column (AD80 manufactured by Showa Denko KK)
6 MS) are connected in series and used.

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. In addition, each of the separated fractions is FT-
It is automatically transported to the IR analyzer. 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
0.4m of solution dissolved in BHT (mg / mL)
Make L injections to create a calibration curve. For the calibration curve, a cubic expression obtained by approximation by the least square method is used. For the conversion to the molecular weight, a general-purpose calibration curve is used with reference to “Size Exclusion Chromatography” by Sadao Mori (Kyoritsu Shuppan). 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> The EP content of the propylene-based block copolymer in the present invention is defined by the following formula (II) and is determined by the following procedure. EP content (% by weight) = W ₄₀ x A ₄₀ / B ₄₀ + W ₁₀₀ x A
₁₀₀ / B ₁₀₀ + W ₁₄₀ x A ₁₄₀ / B ₁₄₀ (II) (W ₄₀ ,
W ₁₀₀ and W ₁₄₀ are the elution ratios (unit:% by weight) of the above-mentioned fractions, and A ₄₀ , A ₁₀₀ and A ₁₄₀ are
It is the average ethylene content (unit weight%) of the actual measurement in each fraction corresponding to W ₄₀ , W ₁₀₀ , W ₁₄₀ , and B ₄₀ , B ₁₀₀ , B ₁₄₀ are the ethylene content of EP contained in each fraction. (Unit:% by weight). A ₄₀ ,
The method for obtaining A ₁₀₀ , A ₁₄₀ , B ₄₀ , B ₁₀₀ , and B ₁₄₀ will be described later. The meaning of the formula (II) is as follows. The first term on the right side of the equation (II) is a term for calculating the amount of EP contained in the fraction 1 (portion soluble at 40 ° C). When the fraction 1 contains only EP and does not contain PP, W ₄₀ contributes to the EP content derived from the fraction 1 as it is in the whole, but the fraction 1 contains a small amount in addition to the components derived from the EP. Since components derived from PP (components having extremely low molecular weight and atactic polypropylene) are also included, it is necessary to correct that portion. Therefore, by multiplying W ₄₀ by A ₄₀ / B ₄₀ , the amount derived from the EP component in the fraction 1 is calculated. For example, the average ethylene content (A ₄₀ ) of fraction 1 is 30% by weight,
Ethylene content (B ₄₀ ) of EP contained in is 40% by weight
In the case of the above, it means that 30/40 = 3/4 (that is, 75% by weight) of the fraction 1 is derived from EP and the remaining 1/4 is derived from PP. In this way, the operation of multiplying A ₄₀ / B ₄₀ in the first term on the right-hand side is based on the weight% of fraction 1 (W ₄₀ ) to EP
Means to calculate the contribution of The same applies to the second and subsequent terms on the right side, and the EP content is calculated by adding the EP contributions for each fraction and adding them together.

(1) As described above, the average ethylene contents corresponding to the fractions 1 to 3 obtained by CFC measurement are A ₄₀ , A ₁₀₀ , and A ₁₄₀ , respectively (units are% by weight). The method for obtaining the average ethylene content will be described later. (2) Determine the ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 (see FIG. 2) as B
₄₀ (unit is weight%). With respect to the fractions 2 and 3, it is considered that the rubber part is completely eluted at 40 ° C., and the same definition cannot be defined. Therefore, in the present invention, B ₁₀₀ = B ₁₄₀ = 100 is defined. B
₄₀ , B ₁₀₀ and B ₁₄₀ are the ethylene content of EP contained in each fraction, but it is practically impossible to analytically determine this value. The reason is that there is no means for completely separating and separating PP and EP mixed in the fraction. As a result of an examination using various model samples, B ₄₀ can successfully explain the effect of improving the physical properties of materials by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. all right. Also, B _100, B _{1 40} is to have a crystallinity of ethylene-derived chain, and two points that relatively small compared to the amount of EP amount of EP contained in these fractions is contained in fraction 1 100 for both reasons
It is closer to the actual situation and there is almost no error in calculation. Therefore, B ₁₀₀ = B ₁₄₀ = 100 is set for analysis.

(3) Determine the EP content according to the following formula
It     EP content (wt%) =     W₄₀× A₄₀/ B₄₀+ W₁₀₀× A₁₀₀/ 100 + W₁₄₀× A₁₄₀/ 100 (II) That is, W, which is the first term on the right side of equation (II)₄₀× A₄₀/ B₄₀
Indicates the EP content (% by weight) having no crystallinity,
W which is the sum of the term and the third term₁₀₀× A₁₀₀/ 100 + W ₁₄₀×
A₁₄₀/ 100 is the crystalline EP content (wt%)
Show. Where B₄₀And each obtained by CFC measurement
Average ethylene content A of fractions 1 to 3₄₀,
A₁₀₀, A₁₄₀Is calculated as follows. Figure 2 is a crystal
Fraction 1 separated by difference in distribution is CFC
The molecular weight distribution can be analyzed by the GPC column that constitutes a part of the analyzer.
Connected behind the measured curve and the GPC column
Corresponding to the molecular weight distribution curve by FT-IR
It is an example showing a distribution curve of the measured ethylene content.
It Ethyl corresponding to the peak position of the differential molecular weight distribution curve
Content of B₄₀Becomes Moreover, in FIG. 2, at the time of measurement
Each data point captured as a data point
Of the weight percentage for each and the ethylene content for each data point
The sum of products is the average ethylene content A₄₀Becomes

The significance of setting the above-mentioned 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 only components that are 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 ethylene crystallinity in EP). The temperature is necessary and sufficient to elute and recover the total amount of the propylene block copolymer used for analysis. Note that the EP component contained in W ₁₄₀ is extremely small and can be practically ignored.

<G and E> Ethylene content in EP (G) (% by weight) = (W ₄₀ × A
_{40 + W 100 × A 100 +} W 140 × A 140) / [EP] However, [EP] is the EP content determined previously (wt%). Of the EP, the ethylene content (E) (% by weight) of the part having no crystallinity was almost 40% in the elution of the rubber part.
Since it is completed at a temperature of not more than 0 ° C, the value of B ₄₀ is approximated.

Requirement (6) Propylene block copolymer
Melting point of the propylene-based block copolymer of the present invention needs to 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. Such high melting point P
To obtain P, a metallocene complex, a cocatalyst, a polymerization condition and the like are appropriately combined and used. 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, the melting point of the block copolymer is approximately PP
It can also be said that the melting point is, and the polymerization reaction in the first step is dominant. Further, the heat resistance of the propylene-based block copolymer strongly depends on the melting point of PP, and the higher the melting point, the higher the improvement. However, on the other hand, even with the same melting point, 8
The larger the loss tangent due to crystal relaxation occurring around 0 ° C., the worse the heat resistance and the high temperature creep resistance. This is because the relaxation of stress against deformation becomes large. Therefore, PP
Is the tan δ at 80 ° C. and the ta at a lower temperature of 50 ° C.
It is preferable that the ratio of nδ is small. Specifically, in order to exhibit good heat resistance, tan δ at 80 ° C. is preferably 4/3 times or less of tan δ at 50 ° C.
Here, tan δ at 50 ° C. and 80 ° C. uses a dynamic viscoelasticity measuring device RDA-II manufactured by Rheometrics, and the temperature is 50 ° C. and 80 ° C. in a geometry of width 12 mm, thickness 3 mm, and length 30 mm. After being stabilized for 5 minutes respectively, the loss elastic modulus E '' and the storage elastic modulus are measured by applying torsional vibration strain with the longitudinal axis as the rotation axis and an angular frequency of 6.28 rad / s and strain of 0.1%. Ratio of E'E "/ E '
That is.

(Iii) Description of Method for Producing Propylene Block Copolymer The method for producing a propylene block copolymer according to the present invention provides a propylene block copolymer satisfying the above physical properties. , But is not particularly limited,
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).

[0038]

[Chemical 1]

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 racemic.

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-mentioned 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-propylphenyl group,
Tri i-propylphenyl group, n-butylphenyl group,
Di-n-butylphenyl group, tri-n-butylphenyl group,
An aryl group such as a t-butylphenyl group, a di-t-butylphenyl group, a tri-t-butylphenyl group, a biphenylyl group, a p-terphenyl group, a m-terphenyl group, a naphthyl group, an anthryl group and a phenanthryl group can be mentioned. Among these, a t-butylphenyl group, a biphenylyl group, a p-terphenyl group, a naphthyl group, an anthryl group and a 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 the halogen is fluorine, chlorine or bromine. For example, in the case of 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-butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-
Butyl fluorophenyl group, fluorobiphenylyl group,
Examples thereof include a fluoro p-terphenyl group, a fluoro m-terphenyl group, a fluoronaphthyl group, a fluoroanthryl group, and a fluorophenanthryl group. 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, a fluoro p-terphenyl group. , Fluoronaphthyl group, fluoroanthryl group, fluorophenanthryl group, t-butylchlorophenyl group, chlorobiphenylyl group, chloro p-terphenyl group, chloronaphthyl group, chloroanthryl group, chlorophenanthryl group are particularly preferable. 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 preferred complex in the component (A) include dimethylsilylenebis (2-ethyl-4-t-butylphenyl-indenyl) zirconium chloride and dimethylsilylenebis (7- (3-phenylindenyl)) zirconium. Dichloride, dimethylsilylenebis (2-isopropyl-4-naphthyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-t-butylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4-) (4-t-butyl-3-chlorophenyl) -4H
-Azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4-phenyl-4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2
-Ethyl-4-naphthyl-4H-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, dimethyl Silylene bis (2-ethyl-4-
(3-chloro-4-t-butyl-phenyl-4H-azulenyl)) hafnium dichloride and the like. Among these, especially dimethylsilylene bis (2-ethyl-
4- (2-Fluoro-4-biphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylene bis (2-ethyl-4- (4-chloro-2-naphthyl-4H)
-Azulenyl)) hafnium dichloride, dimethylsilylene bis (2-ethyl-4- (3-chloro-4-t-butyl-phenyl-4H-azulenyl)) hafnium dichloride are preferred.

<Component (B)> In the present invention, a component selected from the group consisting of the following (b-1) to (b-4) is used as the component (B). (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. 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 silicate include
For example, Haruo Shiramizu, "Clay Mineralogy," Asakura Shoten (1995
The following layered silicates are listed in (1).

That is, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and stevensite, vermiculites such as vermiculite, micas such as mica, illite, sericite and glaucolite, 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 such treatments, by using a lithium compound such as lithium oxide and lithium sulfate treated with sulfuric acid at the same time, a solid catalyst component having a higher melting point and higher activity can be obtained.

<Component (C)> The 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 contacting the above-mentioned components in a (preliminary) polymerization tank at the same time or continuously, or at once or a plurality of 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 amount of the α-olefin used is less than 0.5% by weight based on all the monomers (total of propylene and α-olefin). In the present invention, the α-olefin is
It is a concept of olefin including ethylene and other than propylene. Although PP is preferably a homopolymer of propylene, in the case of producing a copolymer with α-olefin, α-
Ethylene is most preferred as the 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 polymerization temperature is preferably lower. 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 0.1-5M
Pa, preferably 0.1 to 3 MPa. Further, it is preferable to use a molecular weight adjusting agent so that the fluidity (MFR) of the final polymer becomes appropriate, and hydrogen is preferable as the molecular weight adjusting agent.

Propylene-ethylene copolymer component (E
P) Manufacturing Method In the latter polymerization step of the present invention, an ethylene / propylene copolymer having a content weight ratio of propylene and ethylene of 10/90 to 90/10 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 feature of the block copolymer of the present invention is that EP is
It means that the polymer is uniformly and randomly polymerized (the composition distribution is uniform), but in order to produce such a polymer, the following means can be used.

(1) In the process of producing a propylene-ethylene copolymer, the fluctuation of the composition of the polymerization gas over time should be made as small as possible, and the composition of the supply gas (monomer / comonomer ratio) should be kept constant. Generally, when EP is produced, propylene consumed as the polymerization progresses,
It is necessary to supplement the raw material monomer or comonomer corresponding to the amount of ethylene to maintain the same composition as the initial raw material composition. When manufacturing an EP having a uniform composition distribution, it is important to maintain the composition of the raw material gas to be fed with high accuracy. The raw material composition can be maintained by monitoring using a gas chromatograph (GC).

Particularly when a metallocene catalyst capable of producing high melting point PP is used, the propylene monomer has a high polymerizability, so that when propylene-ethylene copolymerization is carried out, propylene is more preferable than ethylene in the mixed gas composition. However, if the result of monitoring is not fed back to the operation of replenishing the raw material promptly, the polymerization will be carried out while the raw material composition deviates from the desired value. For example, when the composition ratio of ethylene becomes temporarily excessive, a polymer having a high ethylene content is produced. In such cases,
This time, the polymer production will be continued with the raw material composition such that the ethylene content will be reduced, and the desired ethylene content will be adjusted in the final product. By suppressing such fluctuations as much as possible, conventional metallocene catalysts and Ziegler
It is possible to secure physical properties better than those of the block copolymer obtained with the Natta (ZN) catalyst system. Further, according to the conventional technical common sense, the raw materials are replenished at the same value as the initial raw material composition on the assumption that the consumption balance due to the polymerization of propylene and ethylene is constant without strictly monitoring by GC or the like.

However, in the present invention, when the polymerization enters a steady state, the initial raw material composition which is generally accepted as the prior art is not maintained, but the raw material having the same propylene / ethylene content ratio of the EP to be produced is used. By maintaining the composition, the consumption and supply of the raw materials by the catalyst can be well balanced, and the consumption and replenishment of ethylene and propylene can be performed without excess or deficiency. It is possible to obtain a block copolymer having physical properties not found. The inventors of the present invention were affected by the history of fluctuations in the raw material composition, and as a result, the composition distribution became non-uniform, resulting in a decrease in the effect of adding rubber that improves impact resistance, and the material physical properties such as rigidity, impact resistance, and luster. It is the fact that it was causing a loss. Another method is to monitor the raw material composition on a feed basis without returning the unreacted raw material used for the polymerization to the reactor again. For example, it is also effective to eliminate the fluctuation of the composition of the polymerization gas by flowing a polymerization gas of a monomer mixture gas of a constant composition in an amount of 10 to 1000 times the production amount of EP, that is, the amount of the consumed monomer.

(2) Use of a metallocene catalyst having a high copolymerizability. By using a specific metallocene catalyst in addition to keeping the raw material composition constant, the randomness of EP can be further enhanced, and the block copolymer of the present subject matter can be produced. The specific metallocene catalyst is a combination of the specific metallocene complex described as preferable in the above with an ion-exchange layered salt subjected to a specific treatment.

(Iv) Description of Composition I Composition I in the propylene resin composition of the present invention is
In the above-mentioned (a) propylene-based block copolymer,
(B) An elastomer is blended. Examples of the elastomer used include ethylene / α-olefin random copolymer rubber and styrene-containing thermoplastic elastomer.

[Ethylene / α-olefin random copolymer rubber] The content of α-olefin unit in the ethylene / α-olefin random copolymer rubber is usually 15 to 70% by weight, preferably 20 to 55% by weight. . If the content of the α-olefin unit is less than the above range, the impact strength is inferior. On the other hand, if the content of the α-olefin unit is too large, not only the rigidity decreases, but also it becomes difficult to maintain the shape of the elastomer in pellet form. Each is unsuitable because the production handling at the time of production is significantly reduced.

The α-olefin has 3 to 20 carbon atoms.
And specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-
Octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene etc. can be mentioned. Among them, propylene, 1-butene, 1-pentene, 1-hexene, 1
-Heptene and 1-octene are preferred.

Further, the MFR (230 ° C., load 21.18) of the above ethylene / α-olefin random copolymer rubber.
N) is usually 0.01 to 100 g / 10 minutes, especially 0.1.
It is preferably about 100 g / 10 minutes. Further, the density is usually 0.85 to 0.90 g / cm ³ , especially 0.86 to
It is preferably 0.89 g / cm ³ .

When the MFR is less than 0.01 g / 10 minutes, sufficient dispersion cannot be obtained at the time of kneading when forming the resin composition, and the impact strength is lowered. on the other hand,
When the MFR exceeds 100 g / 10 minutes, the toughness of the copolymer rubber itself is insufficient, and the impact strength also decreases. Further, when the density is more than 0.90 g / cm ³ , the impact strength becomes poor, and when the density is less than 0.85 g / cm ³ , it is difficult to pelletize itself. Further, these are preferably those produced by using a vanadium compound-based catalyst described later or a metallocene-based catalyst as shown in WO-91 / 04257.

Here, the content of α-olefin is a value measured by a conventional method such as an infrared spectrum analysis method or a ¹³ C-NMR method. The density is a value measured according to JIS-K7112.

Examples of the polymerization method of the ethylene / α-olefin random copolymer rubber include a gas phase fluidized bed method, a solution method, a slurry method and a high pressure polymerization method.
Further, a small amount of a diene component such as dicyclopentadiene or ethylidene norbornene may be copolymerized.

Examples of the polymerization catalyst include titanium compounds such as titanium halides, vanadium compounds, organoaluminum compounds such as alkylaluminum-magnesium complexes and alkylalkoxyaluminum-magnesium complexes.
A so-called Ziegler-type catalyst in combination with a magnesium complex or an organometallic compound such as alkylaluminum or alkylaluminum chloride, or WO-
Examples thereof include metallocene catalysts as disclosed in Japanese Patent Publication No. 91/04257. The catalyst referred to as a metallocene catalyst may not contain alumoxane, but is preferably a catalyst in which a metallocene compound and alumoxane are combined, that is, a so-called Kaminsky catalyst.

Various ethylene / α-olefin random copolymer rubbers are commercially available. For example, as ethylene-propylene rubber, JSR EP02P, EP
07P, EP912P, EP57P etc. (above, manufactured by JSR), Toughmer P0180, P0480, P0680 etc. (above, manufactured by Mitsui Chemicals, Inc.), as ethylene butene rubber JSR EBM2041P, EBM2011P, EBM
3021P etc. (above, manufactured by JSR), Tuffmer A408
5, A4090, A20090, etc. (above, manufactured by Mitsui Chemicals, Inc.) and EG as other ethylene / 1-octene rubbers.
8150, EG8100, EG8200 (above, DuPont Dow Elastomer Co., Ltd., trade name "engage") and the like are commercially available.

[Styrene-Containing Thermoplastic Elastomer] The styrene-containing thermoplastic elastomer used in the present invention has a polystyrene part content of 5 to 60% by weight, preferably 10 to 30%.
It is the one containing wt%. If the polystyrene content is outside the above range, the impact resistance becomes insufficient. Its MFR (230 ° C, load 21.18N) is 0.01
-100 g / 10 minutes, preferably 0.1-50 g / 10
The range of minutes is used. When the MFR is out of the above range, the impact resistance is still insufficient.

Specific examples of such a styrene-containing thermoplastic elastomer include styrene / ethylene / butylene / styrene block copolymer (SEBS). It is a thermoplastic elastomer consisting of polystyrene block units and polyethylene / butylene rubber block units. In such SEBS, the polystyrene block units, which are hard segments, form physical crosslinks (domains) and exist as bridging points of the rubber block units. The rubber block units existing between the polystyrene block units are soft segments. And has rubber elasticity. As the segment ratio of SEBS,
It is desirable to contain the polystyrene unit in an amount of 10 to 40 mol%. The content of the unit derived from styrene is a value measured by a conventional method such as an infrared spectrum analysis method or a 13C-NMR method.

This SEBS is specifically obtained by a known method described in, for example, Japanese Patent Publication No. 60-57463. For such SEBS,
Kraton G1650, G1652, G16
Commercially available products such as 57 (manufactured by Shell Kagaku) and Tuftec (manufactured by Asahi Kasei) can be used.

SEBS used in the present invention is generally SBS which is a styrene / butadiene block copolymer.
(Styrene / butadiene / styrene block copolymer)
Known as hydrogenated product. In the present invention, SBS and other styrene / conjugated diene-based copolymers or complete or incomplete hydrides thereof may be used together with SEBS.

Specific examples of such a styrene / conjugated copolymer include SBR (styrene / butadiene random copolymer), SBS, PS-polyisobutylene block copolymer, SIS (styrene / isobutylene / styrene). Block copolymer) and SIS hydrogenated product (SEPS)
And so on. More specifically, Kraton (Krat
on: manufactured by Shell Chemical Co., Ltd., Calibrex TR (manufactured by Shell Chemical Co., Ltd.), Solbren (manufactured by Phillips Petroleum Co., Ltd.), Eurobren SLT (manufactured by Anitch Co., Ltd.), Toughbren (manufactured by Asahi Kasei Co., Ltd.), Solbren-T (Japan Elastomer). Company), JSRTR (made by JSR), electrified STR
(Manufactured by Denki Kagaku), Quintac (manufactured by Zeon Corporation),
Kraton G (manufactured by Shell Chemical Co., Ltd.), Tuftec (manufactured by Asahi Kasei Co., Ltd.) and the like can be mentioned.

In the present invention, as the elastomer component, the above-mentioned ethylene / α-olefin random copolymer rubber and styrene-containing thermoplastic elastomer may be used alone or in combination thereof.

The composition I of the present invention comprises (a) a propylene block copolymer in an amount of 10 to 99% by weight, preferably 49.
% To 99% by weight, and 1 to 9 of the above (b) elastomer.
0% by weight, preferably 1 to 51% by weight. If the content of the propylene-based block polymer is less than the above range, rigidity, strength and heat resistance are insufficient, and if it exceeds the above range,
Tensile elongation, impact resistance properties, especially low temperature impact resistance properties are insufficient, while when the content of the elastomer is less than the above range, tensile elongation, impact resistance properties, particularly low temperature impact resistance properties are insufficient, and above the above range , Rigidity, strength and heat resistance are insufficient. The composition I of the present invention blended in a predetermined ratio has rigidity,
Good balance of low temperature impact resistance and heat resistance, and excellent overall.

In addition to the above-mentioned essential components (a) and (b), the composition I of the present invention may further contain a polyethylene resin as an optional component, if necessary. As polyethylene resin, Ziegler, chrome,
Examples thereof include those polymerized by a slurry, a gas phase, a solution, a high pressure ion, a high pressure radical polymerization method or the like using a metallocene catalyst or the like.

The polyethylene resin may be an ethylene homopolymer or an ethylene / α-olefin copolymer, of which MFR (190 ° C., load 2)
1.18 N) is 0.1 to 200 g / 10 minutes, and the density is 0.1.
It is preferably 90 to 0.97 g / cm ³ . In the case of ethylene / α-olefin copolymer, specific examples of the α-olefin contained include propylene, 1-butene, 1-
Examples thereof include pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene. Also, ethylene / α-
The content of the α-olefin unit in the olefin copolymer is 0 to 15 mol%.

Specific examples of such polyethylene include high density polyethylene, linear low density polyethylene, and low density polyethylene. The content of the polyethylene resin is preferably 1 to 89 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the composition I. In the present invention, the addition of such a polyethylene resin is preferable, because in addition to rigidity, impact resistance and heat resistance, the adhesive strength with the coating film during coating is improved.

(V) Description of Composition II Composition II in the propylene resin composition of the present invention is
An elastomer and a polypropylene resin produced by using a Ziegler-based catalyst (hereinafter referred to as "Ziegler-based polypropylene") are blended with the above-mentioned propylene-based block copolymer. Specific examples of the elastomer that can be used are the same as those used for the composition I.

Explaining Ziegler type polypropylene, as a specific method for preparing the Ziegler type catalyst, titanium tetrachloride is reduced with an organoaluminum compound,
Furthermore, a method of combining a titanium trichloride composition obtained by treating with various electron donors and electron acceptors and an organoaluminum compound, and a supported catalyst for contacting magnesium tetrachloride with titanium tetrachloride and various electron donors A preparation method and the like can be exemplified.

In the presence of the Ziegler type catalyst thus obtained, propylene alone or block copolymer of propylene and ethylene or propylene and ethylene is applied by applying a manufacturing process such as slurry polymerization, gas phase polymerization or liquid phase bulk polymerization. The Ziegler-type polypropylene of the present invention can be obtained by randomly copolymerizing ethylene.

Of these, when producing a propylene-ethylene block copolymer, homopolymerization of propylene is first performed, and then a block copolymer is formed by random copolymerization of propylene and ethylene, which is of high quality. Is preferred. Further, this propylene-ethylene block copolymer is a ternary or more ternary compound containing other unsaturated compounds, for example, α-olefins such as 1-butene, vinyl esters such as vinyl acetate, etc. within a range that does not impair the effects of the present invention. It may be a copolymer or a mixture thereof.
MFR of this Ziegler type polypropylene (230 ℃,
The load 21.18 N) is preferably 0.01 to 200 g / 10 minutes, and particularly preferably 0.1 to 200 g / 10 minutes.

The composition II of the present invention contains (a) a specific propylene block copolymer produced with a metallocene catalyst in an amount of 10 to 94% by weight, preferably 49 to 89% by weight, and (b) an elastomer. 1 to 85% by weight, preferably 1 to 40% by weight, and 5 to 60% by weight, and preferably 10 to 50% by weight of the above (c) Ziegler type polypropylene. The total amount of (a) propylene block copolymer, (b) elastomer, and (c) Ziegler polypropylene is 100% by weight.

When the content of the propylene block copolymer is less than the above range, rigidity, strength and heat resistance are insufficient, and when it exceeds the above range, tensile elongation, impact resistance, especially low temperature impact resistance is insufficient. To do. If the content of the elastomer is less than the above range, tensile elongation and impact resistance, especially low temperature impact resistance are insufficient, and if it exceeds the above range, rigidity, strength and heat resistance are insufficient. If the content of Ziegler-based polypropylene is less than the above range, moldability such as flow characteristics during melting tends to be insufficient, and if it exceeds the above range, tensile elongation, impact resistance properties, particularly low temperature impact resistance properties are low. Run short. The composition II of the present invention formulated in a predetermined ratio
Has a good balance of rigidity, low temperature impact resistance and heat resistance, and is excellent overall. Moreover, the fluidity is good and the molding processability is improved.

In addition to the above-mentioned essential components, the composition II of the present invention may further contain a polyethylene resin as an optional component, if necessary. Specific examples of the polyethylene resin are the same as the polyethylene resin used as an optional component in the composition I described above.

The content of the polyethylene resin in the composition II of the present invention is 1 to 100 parts by weight of the composition II.
It is preferably 84 parts by weight, and particularly preferably 1 to 40 parts by weight. In the present invention, by adding such a polyethylene resin, in addition to rigidity, impact resistance and heat resistance,
It is preferable because the adhesive strength with the coating film during coating is improved.

(Vi) Other compounding ingredients The propylene resin composition of the present invention (the above-mentioned composition I to
In addition to the above essential components, the following optional additives and compounding agents can be added to II) within a range that does not significantly impair the effects of the present invention or in order to further improve performance. Specifically, pigments for coloring, phenol-based, sulfur-based, phosphorus-based antioxidants, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, and dispersions. Examples include agents, neutralizing agents, foaming agents, copper damage inhibitors, lubricants, flame retardants, various resins other than the above propylene block copolymers, and various rubber components such as polybutadiene and polyisoprene.

Of these, for example, the compounding of various nucleating agents and various rubbers is effective in improving the physical property balance such as rigidity and impact strength and the dimensional stability. For example, the compounding of hindered amine-based stabilizers is effective in weatherability and durability. It is effective in improving sex.

(Vii) Method for Producing Resin Composition The method for producing the propylene resin composition of the present invention is not particularly limited, and the above-mentioned compounding ingredients are compounded into a propylene block copolymer by a conventionally known method, mixed and mixed. It can be produced by melt-kneading.

In the present invention, the above-mentioned essential components, that is, (a) a specific propylene-based block polymer produced by a metallocene catalyst, (b) an elastomer, and (c) a Ziegler-based polypropylene, and if necessary, Arbitrary components and the like to be used are blended in the above blending ratio, and a single screw extruder, a twin screw extruder, a Banbury mixer,
The propylene-based resin composition of the present invention can be obtained by kneading and granulating using an ordinary kneading machine such as a roll mixer, a Brabender plastograph, and a kneader.

In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of each component, and usually a twin-screw extruder is used. During this kneading / granulation, the above-mentioned respective components may be kneaded at the same time, or the respective components may be divided and kneaded in order to improve the performance, that is, for example, first, one of the propylene block copolymers may be mixed. It is also possible to employ a method of kneading all or part of the elastomer with the elastomer, and then kneading and granulating the remaining components.

(Vii) Use of Propylene Resin Composition The propylene resin composition of the present invention thus obtained can be used for molding by various known methods. For example, injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. You can get the goods. this house,
Injection molding and injection compression molding are more preferable.

The injection molded article, the injection compression molded article, the hollow molded article, and the extruded molded article obtained by molding the propylene resin composition of the present invention by the above-described molding method have rigidity, impact resistance, and
As it has a high balance of physical properties in heat resistance,
Various industrial parts field, especially various molded products that are thin, highly functional and large, such as automobile parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tubs, air conditioner parts, vacuum cleaner parts, etc. It has sufficient performance for practical use as a molding material for various industrial parts such as home electric appliance parts.

[0093]

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 used was dehydrated with Molecular Sieve MS-4A. The method and apparatus for measuring each physical property value in the present invention are shown below.

(1) MFR (unit: g / 10 minutes) apparatus Takara Melt Indexer JIS-K6921, temperature 230 ° C., load 21.18
N). In the case of polyethylene resin, JIS-K6922 (temperature 190 ° C, load 21.18)
N). (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) The ethylene content (G) of EP, the ethylene content (E) of the amorphous portion in EP, and the EP content of the whole propylene-based block copolymer were measured according to the methods described above.

(4) Melting point Using a DSC7 type differential scanning calorimeter manufactured by Perkin-Elmer Co., the sample was heated from room temperature to 80 ° C./min at 230 ° C.
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. (5) 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. (6) IZOD impact strength (Unit: kJ
/ M < ² >) It measured at 23 degreeC based on JIS-K7110.

(7) Deflection temperature under load (unit: ° C): 4.6 kgf / cm ² according to JIS-K7207.
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. (8) Gloss (unit:%) Measured at 23 ° C. according to JIS-K7105.

<Polymerization of Propylene Block Copolymer> Polymerization Example 1 (Production of PP-1) [Complex Synthesis] (1) Dichloro {1,1′-dimethylsilylene bis [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 a solution of n-butyllithium in hexane was prepared at -78 ° C. (10.3 mL, 16.6 mm).
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 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. Add and stir. Separately, 581 g (5.93 mol) of sulfuric acid is diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. At this time, part of the sulfuric acid is consumed in the neutralization reaction to form a lithium sulfate salt in the system, and an excess of sulfuric acid causes an acidic solution. There,
Further, 350 g of a commercially available granulated montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm) is added and stirred. After that, heat up to 108 ° C over 30 minutes and
Hold for 50 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 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. 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 2600 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 2.0 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization / Production of Propylene Block Copolymer] 400 mg of triisobutylaluminum and 150 Nm of hydrogen were placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing L and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerized catalyst obtained above in terms of a solid catalyst component was press-fitted to start bulk polymerization of propylene (first stage polymerization). 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, 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, by introducing a propylene / ethylene mixed gas having a composition of ethylene of 35 mol% so as to be equal to the composition of ethylene in the produced EP, the mixed gas composition in the polymerization tank is changed in ethylene mole fraction. 60 mol% was maintained. 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, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered.

100 parts by weight of the obtained powdery propylene block copolymer was used as a compounding ingredient I
RGANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, IRGAFOS 168 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, and calcium stearate 0.05% by weight are blended.
The mixture was kneaded and granulated with a single-screw extruder to obtain a pellet-shaped propylene block copolymer ( PP-1 ).

Polymerization Example 2 (Production of PP-2) In the second-stage polymerization for producing EP of Polymerization Example 1, the composition of the mixed gas introduced at the start of the polymerization was 70 mol% of ethylene, and the mixed gas of 50 mol% of ethylene was introduced during the polymerization. The same polymerization as in Polymerization Example 1 was carried out except that the above was carried out. Less than,
The propylene block copolymer ( PP-2 ) was obtained in the same manner as in Polymerization Example 1.

Polymerization Example 3 (Production of PP-3) 400 mg of triisobutylaluminum, 60 NmL of hydrogen and 750 g of propylene were introduced into a well-dried autoclave equipped with a 3 L stirring blade, and then the temperature in the polymerization tank was kept at 65 ° C. 55 mg of the prepolymerized catalyst used in 1 was converted into a solid catalyst component, and bulk polymerization of propylene was started. Keep the temperature at 65 ° C during the polymerization, and add 100 Nm of hydrogen so that the hydrogen concentration in the gas phase part in the polymerization system becomes constant.
It was continuously introduced at a rate of L / hr. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 85 mol% and the total pressure of the polymerization tank was 1.8 MPa to start the gas phase polymerization of EP. During the polymerization, by introducing a mixed gas having a composition of 70 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank becomes 85 mol% in terms of the ethylene mole fraction. I kept it. 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. Four
After 5 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered. Thereafter, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-3 ).

Polymerization Example 4 (Production of PP-4) Triisobutylaluminum (400 mg), hydrogen (300 NmL) and propylene (750 g) were introduced into a well-dried autoclave equipped with a 3 L stirring blade, and then the temperature in the polymerization tank was set to 65 ° C.
Then, 55 mg of the prepolymerized catalyst used in Polymerization Example 1 in terms of solid catalyst component was press-fitted to start bulk polymerization of propylene. Keep the temperature at 65 ° C during the polymerization, and add 300N hydrogen to keep the hydrogen concentration in the gas phase in the polymerization system constant.
It was continuously introduced at a rate of mL / hr. 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 95 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, by introducing a mixed gas having a composition of 90 mol% of ethylene so as to be equal to the composition of ethylene in the produced EP, the mixed gas composition in the polymerization tank was adjusted to 95 mol% in terms of the ethylene mole fraction. I kept it. 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. Four
After 5 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-4 ).

Polymerization Example 5 (Production of PP-5) After 400 mg of triisobutylaluminum, 90 NmL of hydrogen and 750 g of propylene were introduced into a well-dried autoclave equipped with a 3 L stirring blade, the temperature in the polymerization tank was kept at 65 ° C. 55 mg of the prepolymerized catalyst used in 1 was converted into a solid catalyst component, and bulk polymerization of propylene was started. Keep the temperature at 65 ° C during the polymerization, and add 100 Nm of hydrogen so that the hydrogen concentration in the gas phase part in the polymerization system becomes constant.
It was continuously introduced at a rate of L / hr. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 45 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, by introducing a mixed gas having a composition of 20 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank becomes 45 mol% in terms of the ethylene mole fraction. I kept it. 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. Two
After 0 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-5 ).

Polymerization Example 6 (Production of PP-6) 400 mg of triisobutylaluminum, 100 NmL of hydrogen and 750 g of propylene were introduced into a well-dried autoclave equipped with a 3 L stirring blade, and then the temperature in the polymerization tank was set to 65 ° C.
Then, 55 mg of the prepolymerized catalyst obtained in Polymerization Example 1 in terms of solid catalyst component was press-fitted to initiate bulk polymerization of propylene. Keep the temperature at 65 ° C during the polymerization, and add 100N hydrogen to keep the hydrogen concentration in the gas phase in the polymerization system constant.
It was continuously introduced at a rate of mL / hr. 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 55 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, by introducing a mixed gas having a composition of 30 mol% of ethylene so as to be equal to the composition of ethylene in the produced EP, the composition of the mixed gas in the polymerization tank has a molar fraction of ethylene of 55 mol%. I kept it. 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. 8
After 0 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene-based resin ( PP-6 ).

Polymerization Example 7 (Production of PP-7) A 3 L-round bottom four-necked flask equipped with a vacuum stirrer and a thermometer was charged with 2.0 mol of Mg (OEt) ₂ and then Ti (OBu) ₄ Was charged with Mg (OE
t) ₂ with respect to magnesium in Ti (OBu) ₄ / M
Charged so that g = 0.6 (molar ratio), 200 rp
The temperature was raised while stirring at m. 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 added to magnesium in Mg (OEt) ₂ charged with Si (OPh) ₄ / Mg. = 0.5 (molar ratio). After the addition is completed, the same temperature 1.0
Reacted for hours. After the reaction is completed, the temperature is lowered to room temperature, and then Si
(OEt) ₄ was added to magnesium in the charged Mg (OEt) ₂ so that Si (OEt) ₄ /Mg=0.2 (molar ratio), and a slurry of Ti / Mg contact product was obtained. Got

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 to 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 solid catalyst component (A) thus obtained was Ti.
It contained 2.7 g of propylene polymer per 1 g of Mg contact product. In a well-dried autoclave equipped with a 3 L stirring blade, 550 mg of triethylaluminum and 3 parts of hydrogen were added.
After introducing 000 NmL and 750 g of propylene, the temperature in the polymerization tank was maintained at 70 ° C., and 10 mg of the prepolymerization catalyst obtained above was converted into a solid catalyst component under pressure to start 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 20 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, by introducing a propylene / ethylene mixed gas having a composition of 30 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank is 20 mol% in terms of the mole fraction of ethylene. Kept. Also,
The temperature in the tank during the polymerization is maintained at 75 ° C, and the total pressure is 1.8 MPa.
The mixed gas was introduced so that After 45 minutes,
Unreacted monomer was purged and the autoclave was opened to recover the reacted polymer. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-7 ).

Polymerization of Polymerization Example 8 (PP-8) (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, 1994, 13, 964. (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, a prepolymerized catalyst containing 1.3 g of polypropylene per 1 g of the solid catalyst was obtained. Instead of the prepolymerized catalyst used in Polymerization Example 1, 100 mg of the prepolymerized catalyst synthesized above was introduced in terms of a solid catalyst component, and the mixed gas composition introduced at the start of polymerization in EP polymerization was 30 mol% of ethylene. Ethylene 30
Polymerization was performed in the same manner as in Polymerization Example 1 except that a mixed gas of mol% was introduced. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-8 ).

Polymerization Example 9 (Production of PP-9) In the first step (propylene bulk polymerization) of Polymerization Example 2, 4.75 g of ethylene (0.63% by weight of raw material composition) was used.
The same polymerization as in Polymerization Example 1 was carried out except that the copolymerization was carried out. Hereinafter, polymerization example 1
The propylene block copolymer ( PP-
9 ) was obtained.

Polymerization Example 10 (Production of PP-10) 550 mg of triethylaluminum, 3000 NmL of hydrogen and 750 g of propylene were introduced into a well-dried autoclave equipped with a 3 L stirring blade, and then the temperature in the polymerization tank was kept at 70 ° C. 10 mg of the prepolymerized catalyst obtained in the above was converted into a solid catalyst component, and bulk polymerization of propylene was started. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Furthermore, continuously, propylene and ethylene,
The mixed gas was introduced so that the molar fraction of ethylene was 25 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, ethylene 4 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 of 5 mol%, the mixed gas composition in the polymerization tank was maintained at 25 mol% in terms of the mole fraction of ethylene. Further, the temperature in the tank during the polymerization was kept at 75 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-10 ).

Polymerization Example 11 (Production of PP-11) Triethylaluminum (550 mg), hydrogen (3000 NmL) and propylene (750 g) were introduced into a well-dried autoclave equipped with a 3 L stirring blade, and then the temperature in the polymerization tank was kept at 70 ° C. 10 mg of the prepolymerized catalyst obtained in the above was converted into a solid catalyst component, and bulk polymerization of propylene was started. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Furthermore, continuously, propylene and ethylene,
The mixed gas was introduced so that the mole fraction of ethylene was 30 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, ethylene 5 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 of 5 mol%, the mixed gas composition in the polymerization tank was maintained at 30 mol% in terms of the mole fraction of ethylene. Further, the temperature in the tank during the polymerization was kept at 75 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 30 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered. Then, the same adjustment as in Polymerization Example 1 was carried out to obtain a propylene block copolymer ( PP-11 ).

Various propylene-based block copolymers (PP-1) to (PP-11) produced above, and commercially available propylene-based block copolymers produced by using a Ziegler-Natta catalyst (Novatech PP BC7 (manufactured by Nippon Polychem Co., Ltd.) (hereinafter referred to as PP-12) 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 bending modulus, IZOD impact strength, gloss and deflection temperature under load of the obtained injection-molded piece were measured by the methods described above. The characteristics of (PP-1) to (PP-12) are shown in Table 1.

<Production of Composition of Propylene Block Copolymer and Elastomer> (1) Blending of Resin Component Propylene block copolymer (PP-1) to (PP-
12) was used to produce a propylene resin composition. As the elastomer to be blended with the propylene block copolymer, ethylene / 1-octene copolymer rubber (“Engage 8200” manufactured by DuPont Dow Elastomer Co .; MF
R (230 ° C., load 21.18N): 10 g / 10 minutes,
1-octene content: 24% by weight) was used. These blending components were blended in the blending ratio (% by weight) shown in Table 2, kneaded and granulated with a twin-screw extruder to obtain a pellet-shaped resin composition. (2) Molding of test piece The obtained resin composition 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. About the obtained injection molded piece,
The flexural modulus, IZOD impact strength, and deflection temperature under load were measured by the methods described above. The results are shown in Table 2.

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[Table 1] [Table 1] (Part 1)

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[Table 2] [Table 1] (Part 2)

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[Table 3] [Table 2] (Part 1)

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[Table 4] [Table 2] (Part 2)

The following can be seen from the data of the examples and comparative examples shown in Table 2. (1) The propylene-based resin compositions shown in Examples 1 to 7 have excellent balance between flexural modulus and IZOD impact strength,
It can be seen that the low temperature IZOD impact strength is at a more excellent level if the bending elastic modulus is at the same level. Furthermore, the deflection temperature under load is also high. (2) In contrast, in Comparative Examples 1 to 7, the propylene-based block copolymer was outside the scope of the present invention, and the flexural modulus and IZOD were
The impact strength is not well balanced. (3) Comparative Examples 1 and 3 are inferior in flexural modulus, low temperature IZOD impact strength, and deflection temperature under load to Example 3 while having similar EP content, elastomer content, and MFR. (4) Comparative Example 2 shows a low physical property level of low temperature IZOD impact strength, even though the flexural modulus is equal to or less than that of Examples 1, 2, 4 to 7. (5) Comparative Examples 4 and 5 are inferior in flexural modulus, low temperature IZOD impact strength, and deflection temperature under load to Example 2 while having similar EP content, elastomer content, and MFR. (6) Comparative Example 6 is inferior in flexural modulus, low temperature IZOD impact strength, and deflection temperature under load to Comparative Example 6 while having the same elastomer content and MFR as compared to Example 4. (7) Comparative Example 7 has a lower MFR, lower flexural modulus, low temperature IZOD impact strength, and deflection temperature under load than Comparative Example 2, even though the EP content and elastomer content are similar.

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EFFECTS OF THE INVENTION It has an excellent balance of mechanical strength (especially rigidity, low temperature impact resistance and heat resistance) and is industrially very useful as a molding material for injection molding, extrusion molding and the like. In particular, the improved balance between low temperature impact characteristics and rigidity makes it possible to reduce the thickness and weight of parts in industrial parts applications such as automobile parts, thus improving the fuel efficiency of automobiles. It can contribute to saving energy resources and protecting the global environment, and its industrial value is extremely large.

[Procedure amendment]

[Submission date] December 13, 2001 (2001.12.
13)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 shows a conceptual diagram of CFC-FT-IR.

Figure 2: Fraction 1 (components that elute below 40 ° C)
An example of the differential molecular weight distribution curve of is shown.

[Explanation of Codes] CFC-FT-IR indicates a combined system of a cross fractionation device and a Fourier transform infrared absorption spectrum analysis.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshihiko Kanno             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Co., Ltd. Catalyst Development Center (72) Inventor Masaaki Ito             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Co., Ltd. Catalyst Development Center (72) Inventor Koichi Nakayama             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Material Development Center (72) Inventor Akira Kobayashi             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Material Development Center F-term (reference) 4F071 AA12X AA15 AA15X AA20                       AA22 AA75 AA76 AF05Y                       AF11Y AF20 AF23 AF45                       AH07 AH12 AH17 BB03 BB05                       BB06                 4J002 AC08X BB05X BB12Y BB14Y                       BB15X BC04X BC05X BP02W                       GM00 GN00 GQ00                 4J026 HA04 HA27 HA35 HA39 HA48                       HA49 HB02 HB27 HB35 HB42                       HB43 HB45 HB48 HE02

Claims (3)

[Claims] (A) A metallocene catalyst (a) is used to obtain a propylene polymer component (PP) by a pre-stage process and a propylene-ethylene copolymer component (EP) by a post-stage process. A propylene resin composition comprising 10 to 99% by weight of a propylene block copolymer satisfying 1) to 6) and (b) 1 to 90% by weight of an elastomer. (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 10 to 90% by weight. (5) The relational expression (I) is established between the ethylene content (G) of EP and the ethylene content (E) of a component having no crystallinity in EP. G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G − 7.0 (I) (6) The melting point of the block copolymer is 157 ° C. or higher. 2. (a) Propylene-based block copolymer 10
~ 94 wt%, (b) 1-85 wt% elastomer, and (c) 5-60 wt% polypropylene resin produced using Ziegler-based catalyst. -Based resin composition. 3. A molded product selected from the group consisting of an injection molded product, an injection compression molded product, a hollow molded product, and an extrusion molded product, which is composed of the propylene resin composition according to claim 1. A propylene-based resin molded article characterized in that