JP5089941B2 - Propylene resin composition consisting of three components - Google Patents

Description

  The present invention relates to a propylene-based resin composition, and specifically relates to a three-component resin composition comprising a specific crystalline propylene polymer component and two specific propylene-ethylene copolymer components. Specifically, A crystalline propylene polymer component and two types of propylene-obtained by performing multi-step sequential polymerization using a metallocene-based catalyst capable of highly uniform copolymerization or obtained by blending each component It is a composition comprising an ethylene copolymer, and has the characteristics that rigidity, heat resistance and impact resistance are excellent in a well-balanced manner, and further, impact resistance at low temperature is also improved.

  Propylene-based resins are widely used in the industry as general-purpose resin materials due to their outstanding performance such as moldability, various physical properties, economy, and adaptability to environmental problems. Improvements in compositions with other resin materials such as copolymers with other olefins and olefin-based resins have also been extensively performed.

Propylene resin is very excellent in rigidity, heat resistance, etc., but its impact resistance, which is important as a physical property, is relatively low. As a composition, a technique for improving impact resistance has been well known.
In particular, the composition obtained by a series of polymerization steps is typically obtained by producing a crystalline polypropylene in the first step and a propylene-ethylene copolymer in the second step. Is usually called a propylene-ethylene block copolymer, and exhibits excellent performance in the balance between rigidity and impact resistance, so it is used in many industrial fields including interior and exterior of automobiles. I came.

Such a propylene-ethylene block copolymer is almost industrially produced by using a Ziegler-based catalyst, but Ziegler-based catalysts generally have various active sites (so-called multisite), molecular weight distribution and It is known that the comonomer composition distribution of the propylene-ethylene copolymer part is wide.
In the case of such a propylene-ethylene copolymer having a wide composition distribution, the homogeneity of copolymerization is low, and there are propylene chains or ethylene chains in the copolymer that can be crystallized. These are considered to have an adverse effect on the impact resistance of the block copolymer, and further, the heat resistance deteriorates as a result of the low ethylene content component and low molecular weight component of the copolymer component being dissolved in the crystalline polypropylene component. Has also been pointed out. (See Patent Document 1)

Therefore, an attempt to improve the rigidity, heat resistance and impact resistance in a well-balanced manner by producing a propylene-ethylene block copolymer using a metallocene-based catalyst that has recently been industrially heavily used. Many are made, and a crystalline propylene homopolymer or a copolymer with a small amount of ethylene and a propylene-ethylene copolymer are produced by two-stage polymerization (see Patent Documents 1 to 4).
A metallocene catalyst is characterized by a uniform polymerization active site (single site), and has a narrow molecular weight and comonomer composition distribution as compared to a Ziegler catalyst. Therefore, a more homogeneous and soft rubber component is produced, impact resistance is improved, and compatibility with the crystalline polypropylene component can be controlled, so the above-mentioned problems regarding heat resistance are also considered to be improved. .
However, the narrow composition distribution, on the other hand, reduces the affinity between the crystalline polypropylene component and the propylene-ethylene copolymer component, which adversely affects the particle size and interfacial strength of the copolymer component (elastomer component). Given a simple block copolymer that simply uses a metallocene-based catalyst to produce two components, crystalline polypropylene and a copolymer component, the balance of rigidity, heat resistance, and impact resistance is all well-balanced. Propylene-based block copolymers that give such physical properties are difficult to obtain.

By the way, in order to improve the rigidity, heat resistance and impact resistance of the propylene-based block copolymer in a well-balanced manner, while maintaining sufficient impact resistance by the copolymer component, at the same time, co-polymerization with crystalline polypropylene. It is considered necessary to control the compatibility of the coalescence component within an appropriate range, and the compatibility problem between the polypropylene component and the copolymer component is produced by conventional Ziegler catalysts to varying degrees. It has also been found in propylene-ethylene block copolymers, and a method for increasing the compatibility of these components by adding a polypropylene component and a compatibilizer component in the copolymer part has been known for a long time ( (See Patent Documents 5 and 6). In this technique, a polypropylene component, a propylene-ethylene copolymer component, and a propylene-ethylene copolymer compatibilizer component are polymerized by three-stage polymerization using a Ziegler catalyst.
Recently, in this method, the intrinsic viscosity and MFR of each component are further specified, and a relatively low ethylene content copolymer component and a relatively high ethylene content copolymer component as a crystalline polypropylene component and a compatibilizer. Copolymers that are also excellent in impact resistance at low temperatures are disclosed (see Patent Documents 7 and 8), but in order to improve the balance in physical properties, the ethylene content of each component Even if it is shown that the intrinsic viscosity, that is, molecular weight and even MFR, must be specified within a specific range, Ziegler-based catalysts are used, so a wide molecular weight distribution and composition distribution. The problem described in paragraph 0004 is inherent. In addition, it has been shown that an ethylene-propylene copolymer containing at least 80% by weight of propylene as a compatibilizer component improves impact resistance at low temperatures (see Patent Document 9). .

  Furthermore, recently, like the method using the Ziegler catalyst described above, a metallocene catalyst is used and a propylene-ethylene copolymer compatibilizer component is included to balance rigidity, heat resistance and impact resistance. An attempt has been made to produce an excellent propylene-based resin composition by at least three-stage polymerization (see Patent Document 10). However, in the above-described three-stage polymerization method using a Ziegler-based catalyst, Instead, a metallocene catalyst is used to produce a composition, and only a wide range of component ratios and ethylene contents, as well as a wide range of intrinsic viscosities and MFRs, are specified. It is difficult to say that a production method for a propylene-based resin composition having an excellent impact balance is disclosed.

  Recently, in addition to impact resistance at room temperature, low-temperature (in addition to impact resistance at normal temperature, for frozen food storage packaging materials and industrial materials at low temperatures, as one of higher performance or higher functionality in polypropylene resins. Although there is a strong demand for improvement in impact resistance (cold resistance) of about -30 ° C, even if the improvement in impact resistance at low temperatures is suggested in the previous patent documents 3, 7, and 9 However, it cannot be said that the balance with other physical properties is maintained, and improvement of such physical properties is also desired.

  As outlined above, propylene-based resin materials, which are very important as industrial resin materials, are manufactured using Ziegler-based and metallocene-based catalysts that are very versatile and useful for their production. Even in the propylene-based copolymer for which the technique has been applied, it cannot be said that the rigidity, heat resistance and impact resistance have been sufficiently improved and improved in a well-balanced manner, and the low temperature impact resistance is not necessarily satisfactory. It should be said that these improvements are still awaited.

JP-A-8-67883 (abstract, claims 1, 3, 4 and paragraphs 0002-0004) JP-A-4-337308 (Abstract) Japanese Patent Laid-Open No. 5-202152 (Abstract) JP-A-6-172414 (Summary) JP-A-57-67611 (Claim 1 of the claims) JP-A-61-152442 (claims (1), page 2, lower right column, lines 1 to 2, page 3 upper right column, lower line, line 5 to lower left column, line 2 and Example 1) JP 2003-327642 A (Abstract, Claim 1 and Paragraph 0021) JP-A-9-48831 (summary) Japanese translation of PCT publication No. 2002-501555 (abstract, claim 1 in claims and lines 9 to 10 on page 11) WO95 / 27741 (abstract, claim 1 and page 1, lines 1-3)

  In view of the technical improvement trend in the propylene-based resin materials outlined in paragraphs 0002 to 0009 as background art, it is a recent strong demand to improve the rigidity, heat resistance, and impact resistance in a balanced manner. Since improving impact resistance is not yet fully achieved, the present invention uses a three-stage polymerization production method or a blending process of a propylene resin composition. It is an object of the present invention to solve such improvement in the propylene-based resin material.

  In order to solve such problems in propylene-based resin materials by utilizing a three-stage polymerization method for producing a propylene-based resin composition, the present inventors have determined the type, polymerization conditions, and composition of the polymerization catalyst in three-stage polymerization. About the blending ratio and ethylene content of each component of the product, the compatibility function in the compatibilizer component, various characteristic values such as molecular weight and glass transition temperature, changes in the physical properties of the composition due to the combination of these characteristic values, etc. In order to solve the above-mentioned problems in the process of comparing and demonstrating by experiment, considering and considering in detail from various viewpoints, a propylene composed of a propylene-based polymer and a propylene-ethylene copolymer is used. In the three-stage polymerization or three-component composition of the resin-based resin composition, the compounding ratio of each component of the composition and the ethylene content It is essential to improve compatibilities by setting, to identify each component by TREF method (temperature-elevated solubility fractionation measurement method), and to improve the physical properties of impact resistance by devising the blending ratio of each component and the ethylene content. The present invention was created by realizing the recognition that it is.

The realization of a propylene-based resin composition by a three-stage polymerization method or a three-component blend using the characteristics of a metallocene catalyst, a crystalline polypropylene having specific physical properties, a copolymer component with ethylene, and an ethylene content Specific compatibilizer component (component that improves solubility of crystalline propylene polymer and propylene-ethylene copolymer [sometimes called elastomer]) which is a relatively low specific copolymer This can be done by combination in quantitative ratios, by defining each component using the TREF method, etc., improving the rigidity, heat resistance and impact resistance of the propylene resin material in a well-balanced manner, and also providing impact resistance at low temperatures. We finally realized that we could fully achieve the improvement.
The propylene-based resin composition of the present invention basically includes a propylene homopolymer component or a crystalline propylene polymer comprising a copolymer of propylene and ethylene of up to 3 wt% or an α-olefin having 4 to 20 carbon atoms. Component (a) is composed of 60 to 95% by weight and propylene-ethylene copolymer component (b) is composed of 40 to 5% by weight. Each component is polymerized using a metallocene catalyst, and component (b) is further divided into two components. Is a resin composition in which the quantity ratio of the two components and the ethylene content are defined, and the melting point obtained by differential scanning calorimetry (DSC) and the proportion of the copolymer component determined from TREF are specified.
The basic requirements of such an invention configuration are those whose rationality and significance are demonstrated by contrast with each of Examples and Comparative Examples described later.

  The present invention further includes, as additional requirements, the peak temperature of tan δ derived from the propylene-ethylene copolymer component (b) obtained by solid viscoelasticity measurement, the weight average molecular weight of each component, and the metallocene catalyst used for the polymerization. Or by using an elastomer (rubber component) as another component.

The present invention has been able to sufficiently improve the rigidity, heat resistance and impact resistance of the propylene-based resin material in a well-balanced manner and improve the impact resistance at low temperatures (about -30 ° C). Furthermore, as clarified from the comparison between each example and each comparative example, the impact resistance is improved by characterizing the blending ratio of the two components of a specific propylene-ethylene copolymer. It is characterized by a synergistic increase in sex.
In the propylene resin composition by three-stage polymerization of Ziegler catalyst, impact resistance increases with the increase of the blending ratio of propylene-ethylene copolymer, but it corresponds to the intermediate composition for ethylene content. In contrast, the present invention uses a specific two-component propylene-ethylene copolymer combination, so that the impact resistance is unique due to the blending of the two-component propylene-ethylene copolymer. Can be found. This characteristic is presumed to be due to the very high compatibility of both of the so-called rubber-like (elastomer) copolymer two components and the good affinity at the interface.

By the way, the propylene-based resin composition containing a compatibilizing agent by three-stage polymerization using a metallocene-based catalyst, which is one of the basic requirements of the present invention, is described in paragraph 0010 in the background art above. Upon reviewing the patent literature and other prior art patent literature, Patent Literature 1 (Japanese Patent Laid-Open No. 8-67883) uses a metallocene-based catalyst as a document that can be seen as a description specifically related to the present invention. The invention relates to an invention of a propylene-based resin composition by stage polymerization. In paragraph 0013, an ethylene copolymer of a dispersion accelerator (third component compatibilizer) using a metallocene catalyst may be added by multistage polymerization. Although it is described that it can be done, this description is merely made, and the three-stage polymerization using a metallocene catalyst is not specifically described. I can not find anything. This degree of description can also be found on page 11, lines 16 to 27 of Patent Document 9.
Patent Document 10 (WO95-27741) specifically describes a propylene-based resin composition containing a compatibilizer by three-stage polymerization using a metallocene-based catalyst. Propylene containing at least 80 mol% of propylene having at least three stages of polymerization in the presence, having a melting point of 100 ° C. or higher and an MFR (230 ° C., load 2.16 kg) of 0.01 to 1000 g / 10 min. (Co) polymer component 20 to 90% by weight, propylene in an amount of 50 mol% or more and intrinsic viscosity in the range of 0.1 to 20 dl / g, propylene / olefin copolymer component 5 to 75% by weight, ethylene 50 mol % Of an ethylene / olefin copolymer component having an intrinsic viscosity in the range of 0.1 to 20 dl / g and an MFR of 0.01 The production method of a propylene-based resin composition, which is 500 g / 10 min. ”Is described (summary of claim 1 on pages 97 to 98), and the impact resistance is improved by a compatibilizer (page 49, lines 1 to 3). ) And two-component glass transition temperatures (page 51, line 1, page 53, line 7), the contents of the literature are mostly descriptions of catalyst components and well-known matters. Since the essential description can hardly be found, as described in paragraph 0007 in the background art, the substance of the invention is a composition using a metallocene catalyst instead of a Ziegler catalyst in the three-stage polymerization method using the Ziegler catalyst. A wide range of component ratios and ethylene contents, as well as a wide range of intrinsic viscosities and MFRs, are specified. Specifically, this is a professional product with an excellent balance of rigidity, heat resistance and impact resistance. The a process for Ren resin composition are specifically disclosed in which hardly.
On the other hand, the present invention has specific requirements for a specific configuration in the propylene-based resin composition as described in paragraphs 0013 to 0015, and has an excellent balance of rigidity, heat resistance, and impact resistance. Since the product has a special effect such as a specific improvement in low temperature impact resistance, it can be said that the description of the prior document does not suggest the present invention and does not suggest it.

  In the above, the background of the creation of the present invention, the specific configuration of the invention, the main features, and the comparison with related prior art, etc. have been described generally, so here is a summary of the overall configuration of the present invention. The present invention is composed of the following unit groups of the invention, the one described in [1] is a basic invention, and [2] the following invention adds an additional requirement to the basic invention or forms an embodiment. It is something to do.

（一般式［Ｉ］中において、Ａ^１ 及びＡ^２は、共役五員環配位子〔同一化合物内ではＡ^１ 及びＡ^２ は同一でも異なっていてもよい〕を示し、結合性基Ｑに結合していない共役五員環の炭素は置換基を有してもよく、Ｑは、２つの共役五員環配位子を任意の位置で架橋する結合性基、Ｍは、周期律表４〜６族から選ばれる金属原子を示し、Ｘ及びＹは、それぞれ独立して、Ｍと結合した、水素原子、ハロゲン原子、炭化水素基、アミノ基、ハロゲン化炭化水素基、酸素含有炭化水素基、窒素含有炭化水素基、リン含有炭化水素基又はケイ素含有炭化水素基を示す。）
［７］プロピレン−エチレン共重合体成分（ｂ−１）及び成分（ｂ−２）の配合比により、低温耐衝撃性が相乗して増加されることを特徴とする、［１］〜［６］のいずれかにおけるプロピレン系樹脂組成物。
［８］［１］〜［７］いずれかにおけるプロピレン系樹脂組成物１００重量部に対して、エチレン・α−オレフィン系エラストマー又はスチレン系エラストマー１〜７０重量部を含有することを特徴とするポリオレフィン系樹脂組成物。 [1] A propylene homopolymer component, or a crystalline propylene polymer component (a) composed of a copolymer of propylene and up to 3 wt% of ethylene or an α-olefin having 4 to 20 carbon atoms, and propylene -A propylene-based resin composition comprising an ethylene copolymer component (b) of 40 to 5 wt%, wherein each component is polymerized using a metallocene-based catalyst and satisfies the following characteristics i) to iv).
i) The melting point obtained by differential scanning calorimetry (DSC) is 156 ° C. or higher.
ii) The proportion of the copolymer component (b) obtained from temperature-elevated solubility fractionation measurement (TREF) for fractionation at three levels of 40 ° C., 100 ° C., and 140 ° C. is 5 to 40 wt%.
iii) The ethylene content of the copolymer component (b) determined from temperature-elevated solubility fractionation measurement (TREF) for fractionation at three levels of 40 ° C., 100 ° C., and 140 ° C. is 30 to 50 wt%, The average ethylene content in the components eluted at ~ 100 ° C is 10 wt% or less.
iv) The propylene-ethylene copolymer component (b) comprises at least two types of propylene-ethylene copolymer components (b-1) and components (b-2) having different ethylene contents, and the component (b-1) The ethylene content is 15-30 wt%, the ethylene content of component (b-2) is 40-55 wt%, and the quantitative ratio (b-1) of component (b-1) and component (b-2): (b -2) is in the range of 1:99 to 40:60.
[2] The propylene-based resin composition according to [1], wherein the following property v) is satisfied.
v) The peak temperature of tan δ derived from the propylene-ethylene copolymer component (b) obtained by solid viscoelasticity measurement at a frequency of 1 Hz in the range of -80 to 150 ° C is -47 ° C or lower.
[3] The weight average molecular weights of the component (b-1) and the component (b-2) of the propylene-ethylene copolymer are both 250,000 to 1,000,000, and the weight average molecular weight of the component (a) is The propylene-based resin composition according to [1] or [2], which is 60,000 to 250,000.
[4] The weight average molecular weight of the component (b-1) of the propylene-ethylene copolymer is not less than the weight average molecular weight of the component (b-2), and any one of [1] to [3] Propylene-based resin composition.
[5] Each component is produced by sequential multi-stage polymerization, or individually polymerized components are mixed or produced by combining these steps, [1] to [4] ] The propylene-type resin composition in any one of.
[6] Components (a) and (b) are (A) a transition metal compound represented by the following general formula [I], and (B) (B-1) an organoaluminum oxy compound, (B-2) a transition metal. A compound capable of reacting with a compound to form a cation, (B-3) an activator comprising at least one of ion-exchangeable layered compounds (including silicates) as an essential component, and (C) an organoaluminum compound The propylene-based resin composition according to any one of [1] to [5], wherein the propylene-based resin composition is produced in the presence of a metallocene-based catalyst.

(In the general formula [I], A ¹ and A ² represent a conjugated five-membered ring ligand (in the same compound, A ¹ and A ² may be the same or different), and The carbon of the conjugated five-membered ring that is not bonded may have a substituent, Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M is a periodic table 4 ~ Represents a metal atom selected from Group 6; X and Y are each independently a hydrogen atom, halogen atom, hydrocarbon group, amino group, halogenated hydrocarbon group, oxygen-containing hydrocarbon group bonded to M; , Nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group.)
[7] The low temperature impact resistance is increased in a synergistic manner depending on the blending ratio of the propylene-ethylene copolymer component (b-1) and the component (b-2), [1] to [6] ] The propylene-type resin composition in any one of.
[8] A polyolefin containing 1 to 70 parts by weight of an ethylene / α-olefin elastomer or a styrene elastomer with respect to 100 parts by weight of the propylene resin composition according to any one of [1] to [7]. -Based resin composition.

  The present invention can sufficiently improve rigidity, heat resistance and impact resistance in a propylene-based resin material in a well-balanced manner, and can also improve impact resistance at a low temperature (about -30 ° C). -By specifying the blending ratio of the two components of the ethylene copolymer, there is a remarkable effect that the impact resistance is synergistically increased.

  The outline of the present invention and the skeleton of the structure of the invention have been described above. In the following, embodiments of the invention will be described in detail in order to explain each invention group in the present invention in detail.

1. Regarding Propylene Resin Composition (1) Basic Rules of Resin Composition i) Component The basic rules of the resin composition of the present invention are propylene homopolymer component, propylene and ethylene up to 3 wt%, or 4 to 4 carbon atoms. It consists of a crystalline propylene polymer component (a) 60 to 95 wt% comprising a copolymer with 20 α-olefins and a propylene-ethylene copolymer component (b) 40 to 5 wt%, each component being a metallocene system A propylene-based resin composition that is polymerized using a catalyst. In addition, the mixing | blending of another component is not excluded.

ii) Melting point From the viewpoint of the rigidity and heat resistance of the composition, the propylene resin composition preferably has a higher melting point, preferably 156 ° C or higher, preferably 157 ° C or higher, more preferably 158 ° C or higher. It is.
In order to increase the melting point of the propylene-based resin composition, it is generally necessary to select catalyst components and polymerization conditions so that a propylene-based resin having high stereoregularity can be obtained. The selection of the catalyst component is particularly important, but preferred examples thereof will be described later in paragraph 0048 and thereafter.
In the present invention, the melting point is obtained by differential scanning calorimetry (DSC) measurement. A sample of 5.0 mg is taken, held at 200 ° C. for 5 minutes, and then crystallized at a rate of 10 ° C./min to 40 ° C. Then, the thermal history is erased, and the melting point is the peak temperature of the melting curve when melting at a heating rate of 10 ° C./min. When a plurality of melting points are observed in the resin composition, the one observed at the highest temperature is defined as the melting point of the resin composition.
There is no particular need to define the upper limit of the melting point, but those exceeding 180 ° C. are practically difficult to produce.

(2) Crystalline propylene polymer component (a)
The propylene-based resin composition of the present invention is characterized by excellent rigidity and heat resistance, and for that purpose, the crystalline propylene polymer component (a) (for example, in the case of producing by multistage polymerization, the first stage The polymer produced by polymerization must contain 97% by weight or more of propylene, preferably a polymer containing 99% by weight or more, and most preferably a propylene homopolymer.

(3) Propylene-ethylene copolymer component (b)
i) Mixing ratio In order to impart impact resistance to the propylene-based resin composition of the present invention, the ratio of the propylene-ethylene copolymer component (b) to the entire composition (in the case of producing by multistage polymerization, for example, two The sum of the weights of the components produced by the polymerization after the stage is defined as 40 to 5% by weight. Preferably it is 39 to 6 weight%, More preferably, it is 38 to 7 weight%. Accordingly, the proportion of the crystalline polypropylene component is in the range of 60 to 95% by weight, preferably 61 to 94% by weight, and more preferably 62 to 93% by weight. When the content of the copolymer component exceeds this range, it is inferior in rigidity and heat resistance, and when it is lower, it is inferior in impact resistance.

ii) Measurement of blending ratio and ethylene content (TREF measurement)
A. TREF Method The proportion of the copolymer component (b) can be calculated from the material balance at the time of polymerization, but more specifically, can be determined by a temperature-elevated solubility fractional measurement method (TREF).
The technique for evaluating the crystallinity distribution of the block copolymer by TREF is well known to those skilled in the art, and for example, the following literature shows a detailed measurement method.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Po
lym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36,
8, 1639-1654 (1995)
In TREF measurement, the lower the crystallinity, the lower the elution, and the higher the crystallinity, the higher the elution, so it is possible to accurately grasp the distribution of the crystallinity of the polypropylene resin. .

B. Measurement by TREF In the method of TREF in the present invention, specifically, as described below, the fractionated fractions are analyzed by an apparatus combining GPC and FT-IR, thereby simultaneously measuring each molecular weight and ethylene content. It is possible to determine various characteristic values (indexes) of the propylene resin composition. Details of this method are described in Japanese Patent Application Laid-Open No. 2003-147035, but a specific procedure will be simply described below.

a. Analytical device to be used [Cross separation device]
Diamond Instruments CFC T-100 (abbreviated as CFC)
[Fourier transform infrared absorption spectrum analysis]
FT-IR Perkin Elmer 1760X
A fixed wavelength infrared spectrophotometer attached as a CFC detector is removed and an FT-IR is connected instead, and 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 is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. 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 the temperature is maintained at 140 ° C. throughout the measurement.
[Gel permeation chromatography (GPC)]
The GPC column at the latter stage of the CFC is used by connecting three AD806MS manufactured by Showa Denko in series.

b. CFC measurement conditions Solvent: Orthodichlorobenzene (ODCB) Sample concentration: 4 mg / mL
Injection amount: 0.4 mL Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes. Fractionation method: Fractionation temperature during temperature elution fractionation is 40, 100, and 140 ° C., and fractionation is performed in all three 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), respectively It is defined as W ₄₀ , W ₁₀₀ , and W ₁₄₀ . W ₄₀ + W ₁₀₀ + W ₁₄₀ = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is. Solvent flow rate during elution: 1 mL / min

c. Measurement conditions of FT-IR After elution of the sample solution starts from GPC at the latter stage of the CFC, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3.
Detector: MCT Resolution: 8 cm ⁻¹ Measurement interval: 0.2 minutes (12 seconds) Integration count per measurement: 15 times

d. Post-processing and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are determined using the absorbance at 2,945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
[When creating a calibration curve using standard polystyrene]
K = 1.38 × 10 ⁻⁴ α = 0.70
[When measuring sample of propylene-ethylene block copolymer]
K = 1.03 × 10 ⁻⁴ α = 0.78
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each elution component was determined by using the ratio of the absorbance at 2,956 cm ^{−1 and} the absorbance at 2,927 cm ⁻¹ obtained by GPC-IR. Ethylene content (weight) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) and a mixture thereof whose ethylene content is known by polypropylene, ¹³ C-NMR measurement, etc. %).

C. Theoretical calculation of copolymer content The content of the copolymer component (b) in the propylene-based resin composition in the present invention is defined by the following formula (I), and is determined by the following procedure.
Copolymer component content (wt%) =
W ₄₀ × A ₄₀ / B ₄₀ + W ₁₀₀ × A ₁₀₀ / B ₁₀₀ (I)
W ₄₀ and W ₁₀₀ are elution ratios (unit:% by weight) in each of the above-mentioned fractions, and A ₄₀ and A ₁₀₀ are average ethylene contents (units: in each fraction corresponding to W ₄₀ and W _100). B ₄₀ and B ₁₀₀ are the ethylene content (unit: wt%) of the copolymer component contained in each fraction. A method for _obtaining A ₄₀ , A ₁₀₀ , B ₄₀ , and B ₁₀₀ will be described later.
The meaning of the formula (I) is as follows. The first term on the right side of the formula (I) is a term for calculating the amount of the copolymer contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only a copolymer and does not contain PP (propylene polymer), W ₄₀ contributes to the copolymer content derived from fraction 1 as a whole, but fraction 1 Since a small amount of PP-derived components (extremely low molecular weight components and atactic polypropylene) are included in addition to the copolymer-derived components, it is necessary to correct that portion. Therefore, by multiplying W ₄₀ by A ₄₀ / B ₄₀ , the amount derived from the copolymer component in fraction 1 is calculated. For example, when the average ethylene content (A ₄₀ ) of fraction 1 is 30% by weight and the ethylene content (B ₄₀ ) of the copolymer contained in fraction 1 is 40% by weight, 30/40 of fraction 1 = 3/4 (that is, 75% by weight) is derived from the copolymer, and the remaining 1/4 is derived from PP. Thus, the operation of multiplying A ₄₀ / B ₄₀ by the first term on the right side means that the contribution of the copolymer is calculated from the weight% of fraction 1 (W ₄₀ ). The same applies to the second term on the right side, and for each fraction, the copolymer content is calculated and added to calculate the contribution of the copolymer.

D. Actual measurement of copolymer content Average ethylene contents A ₄₀ and A _{100 in} fractions 1 to 3 are the weight ratio for each data point and the ethylene content for each data point in the chromatogram of absorbance at 2,945 cm ^−1. obtained by summation of the product of (obtained from the ratio between the absorbance and the absorbance of 2,927Cm ^-1 of 2,956cm ^-1).
The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B ₄₀ (unit is% by weight). For fractions 2 and 3, it is considered that the rubber part is completely eluted at 40 ° C. and cannot be defined with the same definition, so in the present invention, it is defined as B ₁₀₀ = 100. B ₄₀ and B ₁₀₀ are the ethylene content of the copolymer contained in each fraction, but it is practically impossible to determine this value analytically. The reason is that there is no means for completely separating and separating PP and EP mixed in the fraction. As a result of studies using various model samples, B ₄₀ can rationally explain the effect of improving material properties when the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1 is used. I understood that I could do it. In addition, B ₁₀₀ has crystallinity derived from ethylene chain, and the amount of copolymer contained in these fractions is relatively small compared to the amount of copolymer contained in fraction 1. For the reason, approximating 100 is closer to the actual situation and hardly causes an error in calculation. Therefore, the analysis is performed with B ₁₀₀ = 100.
Accordingly, the content of the copolymer component (b) can be determined according to the following formula.
Copolymer component content (wt%)
_{= W 40 × A 40 / B} 40 + W 100 × A 100/100 (II)
That is, W ₄₀ × A ₄₀ / B ₄₀ which is the first term on the right side of the formula (II) indicates the content (% by weight) of the copolymer component having no crystallinity, and W ₁₀₀ × A ₁₀₀ which is the second term. / 100 indicates the content (% by weight) of a copolymer component having crystallinity.
The ethylene content in the copolymer component is determined by the following formula using the content of the copolymer component determined by the formula (II).
Ethylene content (% by weight) in copolymer component
= (W ₄₀ × A ₄₀ + W ₁₀₀ × A ₁₀₀ ) / [Copolymer component content] (III)

  The significance of setting the three types of fractionation temperatures is as follows. In the CFC analysis of the present invention, only a polymer having no crystallinity at 40 ° C. (for example, most of copolymer components, or extremely low molecular weight components and atactic components among propylene polymer components (PP)) It has the meaning that it is a temperature condition necessary and sufficient for fractionation. 100 ° C. is a component that is insoluble at 40 ° C. but becomes soluble at 100 ° C. (for example, a component having crystallinity due to a chain of ethylene and / or propylene in a copolymer component, and low crystallinity) The temperature is necessary and sufficient to elute only PP). 140 ° C. is a component that is insoluble at 100 ° C. but becomes 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 a copolymer component) ) Only, and the temperature is necessary and sufficient to recover the entire amount of the propylene-based resin composition used for the analysis.

iii) Ethylene content The ethylene content in the copolymer component (b) can be determined from the material balance at the time of polymerization, but it is also preferably determined by the above-mentioned method, and the viewpoint of imparting low-temperature impact to the block copolymer Therefore, the range needs to be 30 to 50 wt%, preferably 32 to 47 wt%, and more preferably 35 to 43 wt%. If it is below this range, the impact resistance at low temperature is poor, and if it exceeds, the compatibility between the PP component and the copolymer component is too low, and the impact resistance is also poor.

(4) Characteristics of ethylene content ratio and blending ratio in copolymer two components i) Basic characteristics The essential characteristic of the propylene-based resin composition of the present invention is that propylene-ethylene random copolymer component (b) is It consists of at least two-component propylene-ethylene random copolymers having different ethylene contents, and the ethylene content ratio and blending ratio in the two copolymer components are specified. Due to this feature, ie, as emphasized in paragraph 0015, the remarkable effect is that the impact resistance is synergistically increased by the characterization of the blending ratio in the propylene-ethylene copolymer binary component having a specific ethylene content. It is what.

  The copolymer component (b) includes a copolymer component (b-2) composed of a propylene-ethylene copolymer having a relatively high ethylene content and a phase composed of a propylene-ethylene copolymer having a relatively low ethylene content. The two components of the solubilizer component (b-1) are essential components. As long as other various conditions are satisfied, the component (b-1) and the component (b-2) may each be a composition comprising a plurality of components, but from the viewpoint of production cost, the crystalline polypropylene component It is preferable to use three components: a compatibilizer component having a low ethylene content and a copolymer component having a high ethylene content.

  In order to improve the overall physical property balance of the propylene-based resin composition, the ethylene content and the quantity ratio of the components (b-1) and (b-2) in the copolymer component are defined in more detail. Component (b-2) is a copolymer component necessary for imparting low-temperature impact resistance to the propylene-based resin composition, and component (b-1) is a propylene polymer component and a high ethylene content component. It is a compatibilizer component. In particular, when using a metallocene catalyst as in the present invention, the compatibilizer component is more important because the molecular weight distribution and the composition distribution of the copolymer are narrower than when using a Ziegler catalyst, and in particular, the compatibilizer component. Therefore, it is necessary to define more precise characteristic values (indexes).

ii) Regulation of ethylene content From the above consideration, in the propylene-based resin composition of the present invention, the ethylene content of component (b-1) which is a compatibilizing agent component is 15 to 30 wt%. Preferably it is the range of 15-25 wt%. When the ethylene content is below this range, the compatibility with the component (b-2) is poor, and when it is above the compatibility with the component (a), the performance as a compatibilizer is sufficient in both cases. Can not be demonstrated.

In addition, Japanese Patent Publication No. 2002-501555 (Patent Document 9 cited in paragraph 0010) of the prior document discloses an ethylene-propylene copolymer having a propylene content of at least 80% by weight as a compatibilizer component. However, when the contents are scrutinized, the ethylene content of the compatibilizer component is in a relatively low numerical range of 8.5-13 wt%. In the specification page 23 and FIG. 3, the form of fracture in the impact test when the compatibilizer component is added is explained as stretched rubber particles without signs of cavitation. It can be inferred from these results that the compatibilizing agent component is mainly contained in the homopolypropylene as a matrix, and the physical properties thereof are more plastically modified. However, such a compatibilizer component having an ethylene content that is too low has a significant adverse effect of lowering rigidity by being compatible with the matrix polypropylene, and the compatibilizer is too low because the ethylene content is too low. The glass transition temperature of the component is high, and as a result, improvement of impact strength of the whole composition, particularly at low temperatures, cannot be achieved.
That is, as a compatibilizing agent component, both a crystalline propylene polymer (component (a) in the present invention) and a copolymer having a high ethylene content (component (b-2) in the present invention) as a matrix are used. A component that has a certain degree of affinity but is not completely compatible is preferable. Also from this viewpoint, in the present invention, the lower limit of the ethylene content of the component (b-1) as the compatibilizer component needs to be 15 wt%.

  Whether or not the solubilizer component is preferentially compatible with the crystalline propylene polymer component as a matrix can be determined by measuring the glass transition temperature of the entire composition. In the range of the ethylene content of the compatibilizer component as defined in the present invention, the compatibilizer component is only slightly compatible with the crystalline propylene polymer component, so the glass transition temperature of the crystalline propylene polymer is Does not change much compared to the case where no compatibilizer component is added. On the other hand, when the ethylene content of the compatibilizer component is below the range of the present invention, most of the compatibilizer component is compatible with the crystalline propylene polymer, so that the glass transition temperature of the crystalline propylene polymer is as described above. It is detected as a value several degrees (° C.) lower than The glass transition temperature of the crystalline propylene polymer is defined as the peak position detected in the temperature range of about −10 to 10 ° C. in the loss tangent-temperature profile obtained from solid viscoelasticity measurement (DMA). . The above phenomenon is manifested in the comparison of each example and each comparative example in Table 6 described later.

The ethylene content of component (b-2) is 40 to 55 wt%. Preferably it is 41-53 wt%, More preferably, it is the range of 42-50 wt%. When the ethylene content is outside this range, the glass transition temperature of the copolymer component becomes high, and sufficient low temperature impact resistance cannot be obtained.
The ethylene content is controlled by adjusting the amount of ethylene supplied in the polymerization reaction or by selecting a blend component.

iii) Definition of the quantitative ratio of the two components The quantitative ratio of the component (b-1) and the component (b-2) is (b-1) :( b-2) = 1: 99 to 40:60. It is preferable in terms of balance of physical properties. Preferably it is the range of 5: 95-35: 65, More preferably, it is the range of 10: 90-30: 70. When the amount ratio of the component (b-1) is below this range, the effect as a compatibilizing agent is reduced, and sufficient impact resistance cannot be obtained at both room temperature and low temperature. This is not preferable because the content of the amount becomes too small and the low-temperature impact resistance is impaired.
The ethylene content and quantity ratio of the components (b-1) and (b-2) were determined by separately preparing the components (a), (b-1) and (b-2) and kneading the resin composition. In this case, the ethylene content of each component is determined in advance, and the amount ratio can be controlled by the kneading amount ratio. In the case of producing by multistage polymerization, it can be determined by the material balance of the polymerization process, analysis of the sample taken during the polymerization, or measurement by TREF-IR described above.

(5) Identification of polymerization catalyst The block copolymer of the present invention requires precise index control in the ethylene content, blending ratio and other regulations of the two components of the copolymer. For this purpose, the molecular weight distribution of the polymer is required. In addition, it is necessary that the copolymer composition be produced with a metallocene catalyst that is narrow and uniform. The advantages obtained in the physical properties when a block copolymer is produced using a metallocene catalyst are, as already described in detail, from the viewpoint of the polymer structure by TREF, as well as from the block copolymer by a conventional Ziegler catalyst. Is also obvious. That is, when a block copolymer is produced with a metallocene catalyst, there is almost no structure derived from the crystallinity of polyethylene in component (b) that adversely affects impact resistance. Therefore, the block copolymer of the present invention is characterized in that the average ethylene content A ₁₀₀ in the dissolved component at 40 to 100 ° C. is 10 wt% or less, preferably 5 wt% or less, in TREF of the above-described method. More preferably, it is 1 wt% or less.

(6) Glass transition temperature (tan δ peak temperature) Usually, from the viewpoint of impact resistance at low temperatures of the propylene resin composition, the glass transition temperature should be sufficiently low as a whole of the propylene resin composition. In addition to defining the average ethylene content of the copolymer, it is necessary to define the glass transition temperature. In the propylene-based resin composition of the present invention, it is obtained by a solid viscoelasticity measurement that detects a stress generated by applying a sinusoidal strain to a strip-shaped sample piece in a range of −80 to 150 ° C. and a frequency of 1 Hz. The glass transition temperature (so-called tan δ peak temperature) of the polymer component is preferably −47 ° C. or lower, more preferably −49 ° C. or lower. When the glass transition temperature is higher than this, the impact resistance at low temperatures is poor. The lower limit of the glass transition temperature does not need to be specified in particular, but in fact, it is difficult to produce those having a temperature of -70 ° C or lower.

In the measurement of the solid viscoelasticity of the block copolymer, generally, the glass transition temperature derived from the amorphous part of the crystalline PP is around −10 to 10 ° C., and the glass transition derived from the copolymer component. Although the temperature is observed at a lower temperature (generally −10 ° C. or lower), the glass transition temperature here is derived from the copolymer component. When a plurality of glass transitions derived from the copolymer component are observed, the glass transition temperature is observed at a lower temperature.

(7) Definition of molecular weight i) Identification of molecular weight of each component The weight average molecular weight (Mw) of component (b-1) and component (b-2) is in the range of 250,000 to 1,000,000. It is preferable. More preferably, it is 270,000-900,000, More preferably, it is the range of 300,000-800,000. If the molecular weight is below this range, the impact resistance and rigidity are inferior.
Moreover, it is preferable from a viewpoint of impact resistance that the weight average molecular weight of a component (b-1) is more than the weight average molecular weight of a component (b-2). Although it is not clear about this reason, since a component (b-1) plays the role which reinforces the interface of a component (a) and a component (b-2) as a compatibilizer component, it is a component with higher molecular weight. This is probably because more entanglements are formed between (a) and (b-2), and the strength of the interface can be further increased. The range of the weight average molecular weight of the component (a) is preferably lower than that of the component (b) and 250,000 or less from the viewpoint of imparting the fluidity necessary for molding to the block copolymer. Is preferred. Since the embrittlement occurs when the molecular weight is too low, the molecular weight is preferably 60,000 or more. A more preferable range is 220,000 to 70,000, and a further preferable range is 200,000 to 80,000.

ii) Measurement of molecular weight
In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC), and is obtained by measuring at a temperature of 140 ° C. using orthodichlorobenzene as a solvent. Conversion to molecular weight is performed by conversion using a standard polystyrene sample.
The molecular weight of each component can be determined from the molecular weight measurement of each component when produced by kneading, and when produced by multistage polymerization, it can be determined by calculation from analysis by GPC of a sample taken during polymerization, Or it can also determine from the molecular weight data in the above-mentioned TREF-GPC-IR measurement.
In the TREF-GPC-IR measurement, the polymer is fractionated into 40, 100, and 140 ° C. elution components, and the average molecular weight and molecular weight distribution can be calculated. In order to accurately define the molecular weight of the copolymer, the low molecular weight or low regularity polypropylene component originally present in the 40 ° C. soluble part, or 40 ° C. It is necessary to make calculation corrections for copolymer components that dissolve at temperatures above that. However, as already described, when a block copolymer is polymerized using a metallocene catalyst, the copolymer component Most of them are present in the 40 ° C. soluble component, and the amount of low molecular weight or low regularity polypropylene component produced is extremely small, so calculation correction is not necessary. Therefore, in this invention, when determining the molecular weight of a copolymer by TERF-GPC measurement, the weight average molecular weight of a 40 degreeC soluble part is defined as the weight average molecular weight of a copolymer component as it is.
Regarding the weight average molecular weight of the propylene polymer component, it is necessary to calculate and correct the elution amount of the polypropylene polymer component at 40 ° C. and 100 ° C., which is the weight average molecular weight of the entire composition and the weight average molecular weight of the copolymer component. And if content of a propylene resin component is understood, it can obtain | require with an addition rule.

2. Production of polypropylene resin composition (1) Metallocene catalyst
As described above, it is preferable that all the components of the resin composition of the present invention are produced by a metallocene catalyst, but a metallocene copolymer having a higher melting point and excellent heat resistance and rigidity is obtained. In order to produce industrially easily and inexpensively, [A] a transition metal compound represented by the following general formula [I], and [B] (B-1) an organoaluminum oxy compound, disclosed below, An activator comprising at least one of (B-2) a compound capable of reacting with a transition metal compound to form a cation and (B-3) an ion-exchange layered compound (including silicate) is an essential component. [C] It is preferable to use a catalyst containing an organoaluminum compound as an optional component, and among them, it is most preferable to use a catalyst comprising the above [A] and (B-3) and an organoaluminum compound as an optional component. Preferred.

一般式［Ｉ］中、Ａ^１ 及びＡ^２は、共役五員環配位子（同一化合物内においてＡ^１ 及びＡ^２ は同一でも異なっていてもよい）を示し、そして、Ａ^１及びＡ^２ の共役五員環配位子は、結合性基Ｑに結合していない炭素に置換基を有していてもよい。 A. [A] Transition metal compound The transition metal compound mainly used in the present invention is a metallocene complex represented by the following formula.

In the general formula [I], A ¹ and A ² represent conjugated five-membered ring ligands (A ¹ and A ² may be the same or different in the same compound), and A ¹ and A ² The conjugated five-membered ring ligand may have a substituent on carbon not bonded to the binding group Q.

Typical examples of the conjugated five-membered ring ligand include a cyclopentadienyl group. This cyclopentadienyl group may have 4 hydrogen atoms, and as described above, some of the hydrogen atoms may be substituted with substituents. One specific example of the above substituent is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, phenyl group, naphthyl group, butenyl group, butadienyl group, and triphenylcarbyl group.
The hydrocarbon group may be bonded to the cyclopentadienyl group as a monovalent group, and two types may be bonded at the end of the substituent to form a condensed ring. Typical examples of the cyclopentadienyl group having a condensed ring include compounds such as indene, fluorene, and azulene, and derivatives thereof. Among these, indene, azulene and derivatives thereof are more preferable, and among them, azulene is most preferable.
Examples of the substituent other than the hydrocarbon group include hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Typical examples include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like.
Examples of other substituents include a halogen atom or a halogen-containing hydrocarbon group. Typical examples thereof include chlorine, bromine, iodine, fluorine, trichloromethyl group, trifluoromethyl group, fluorophenyl group, pentafluorophenyl group and the like.

By the way, the feature of the transition metal compound used in the present invention is that at least one of A ¹ and A ² is bonded to an adjacent substituent on the conjugated five-membered ring ligand and includes two atoms of the five-membered ring. It is in the point which has a 7-10 membered condensed ring. That is, either ^one of A ¹ and A ² can form a 7 to 10 condensed ring including at least two adjacent carbon atoms of a conjugated five-membered ring. The carbon of the condensed ring may be saturated or unsaturated except for two atoms of the conjugated five-membered ring.

For example, the above ligands constituting A ¹ and A ² include hydroazurenyl group, methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropyl Hydroazurenyl group, methylphenylisopropylhydroazurenyl group, hydrogenated product of various azulenyl groups, bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl -Bicyclo- [6.3.0] -undecanyl group, phenyl-bicyclo- [6.3.0] -undecanyl group, methylphenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -Undecanyl group, methyldiphenyl-bicyclo- [6.3.0] -undecanyl Methyl-bicyclo- [6.3.0] -undecadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.3.0] -undecadienyl group, methylisopropyl -Bicyclo- [6.3.0] -undecadienyl group, bicyclo- [7.3.0] -dodecanyl group and derivatives thereof, bicyclo- [7.3.0] -dodecadienyl group and derivatives thereof, bicyclo- [8 .3.0] -tridecanyl group and derivatives thereof, bicyclo- [8.3.0] -tridecadienyl group and derivatives thereof, and the like.
Examples of the substituent for each group include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur, halogen atoms, or halogen-containing hydrocarbon groups.

Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group and crosslinks A ¹ and A ² .
The type of Q is not particularly limited, and specific examples thereof include (a) a divalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, An unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, and an arylene, a haloalkylene group, a halocycloalkylene group, (b) a silylene group or an oligosilylene group, and (c) a carbon number of usually 1 to 20, preferably 1 to A silylene group or an oligosilylene group having 12 hydrocarbon groups or halogenated hydrocarbon groups as a substituent, (d) germylene group, (e) a hydrocarbon group or halogenated hydrocarbon group usually having 1 to 20 carbon atoms. Examples thereof include a germylene group as a substituent.
In these, the silylene group or germylene group which has an alkylene group, a cycloalkylene group, an arylene group, and a hydrocarbon group as a substituent is preferable.

  M represents a transition metal atom selected from groups 4 to 6 of the periodic table (short-period type), preferably a group 4 transition metal of titanium, zirconium or hafnium, more preferably zirconium or hafnium. Particularly preferred is hafnium.

X and Y are each independently a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. Or a silicon-containing hydrocarbon group is shown.
Carbon number in each said hydrocarbon group is 1-20 normally, Preferably it is 1-12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamino group, and a diethylamino group are preferable.

As specific examples of the transition metal compound in the present invention, since the block copolymer of the present invention is excellent in rigidity and heat resistance, the following compounds are particularly preferable. In addition, although description of a compound is only designated only with the chemical name, the three-dimensional structure means both the compound with asymmetry and the compound with symmetry as used in the present invention.
(1) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4H-azulenyl}] zirconium, (2) Dichloro [1,1′-dimethylsilylenebis {2-methyl -4- (4-t-butylphenyl) -4H-azurenyl}] hafnium, (3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4H -Azurenyl}] hafnium, (4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-5,6,7,8-tetrahydroazurenyl}] Hafnium, (5) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium, (6) dichloro 1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-5,6,7,8-tetrahydroazurenyl}] hafnium, (7) dichloro [1,1 '-Dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4H-azulenyl}] hafnium, (8) dichloro [1,1'-dimethylsilylenebis {2-ethyl- 4- (3-chloro-4-trimethylsilylphenyl) -4H-azurenyl}] hafnium, (9) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3-methyl-phenyl) ) -4H-azulenyl}] hafnium, (10) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3,5-dichloro) -Phenyl) -4H-azulenyl}] hafnium, (11) dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl}] hafnium (12) dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dimethylphenyl) -4H-azurenyl}] hafnium and the like.

One or both of the dichlorides forming the X and Y moieties in the compound as described above are a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isobutyl group, a phenyl group, a fluorophenyl group, a benzyl group, Examples also include compounds substituted for a methoxy group, a dimethylamino group, a diethylamino group, and the like. In addition, compounds in which the central metal of the compound exemplified above is replaced with titanium, tantalum, niobium, vanadium, tungsten, molybdenum or the like instead of zirconium or hafnium can be exemplified.
Among these, a group 4 transition metal compound of zirconium, titanium, and hafnium is preferable, and hafnium is particularly preferable among them.
These [A] components may be used in combination of two or more. In addition, the [A] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

B. [B] Cocatalyst (activator component)
In the present invention, as the component [B], (B-1) an organoaluminum oxy compound,
(B-2) An activator comprising at least one of a compound capable of reacting with a transition metal compound to form a cation and (B-3) an ion-exchange layered compound (including silicate) is used. It is done.

上記各一般式中、Ｒ^１は水素原子又は炭化水素基、好ましくは炭素数１〜１０、特に好ましくは炭素数１〜６の炭化水素基を示す。また、複数のＲ^１はそれぞれ同一でも異なっていてもよい。また、ｐは０〜４０、好ましくは２〜３０の整数を示す。
一般式のうち、一番目及び二番目の式で表される化合物は、アルミノキサンとも称される化合物であって、これらの中では、メチルアルミノキサン又はメチルイソブチルアルミノキサンが好ましい。上記のアルミノキサンは、各群内及び各群間で複数種併用することも可能である。そして、上記のアルミノキサンは、公知の様々な条件下に調製することができる。
一般式の三番目で表される化合物は、一種類のトリアルキルアルミニウム又は二種類以上のトリアルキルアルミニウムと、一般式Ｒ^２Ｂ（ＯＨ）_２で表されるアルキルボロン酸との１０：１〜１：１（モル比）の反応により得ることができる。
一般式中、Ｒ^１及びＲ^２は、炭素数１〜１０、好ましくは炭素数１〜６の炭化水素基を示す。 In the present invention, the (B-1) organoaluminum oxy compound specifically includes compounds represented by the following general formulas.

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

  In the present invention, as a compound capable of reacting with the transition metal compound (B-2) to form a cation, an ionic property capable of reacting with the component [A] to convert the component [A] into a cation. A compound or Lewis acid is used. As such an ionic compound, a cation such as a carbonium cation or an ammonium cation and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron are used. Examples include complexed products.

Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with component [A] and convert component [A] into a cation.
The reaction product of the above components [A] and (B-1) or the reaction product of components [A] and (B-2) should be used as a catalyst supported on a particulate carrier such as silica. Is most preferred.

In the present invention, (B-3) an ion-exchange layered compound (including silicate) is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force. Ions can be exchanged. Examples of the ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.
Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H. ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, y-Zr (HPO ₄ ) ₂ , y-Ti Examples thereof include crystalline acidic salts of polyvalent metals such as (HPO ₄ ) ₂ and y-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used. Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Smectites such as stones, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, etc., attapulgite, sepiolite, pygorskite, bentonite , Kibushi clay, gyrome clay, hysingelite, pyrophyllite, chlorite and the like. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

  Of these specific examples, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, serpentine groups such as chrysotile, lizardite and antigolite, montmorillonite, zauconite and beidellite. , Smectites of nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, chlorophyll, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, especially Preferably, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hector Ito, synthetic saponite, synthetic taeniolite.

These ion-exchangeable layered compounds may be used as they are, but are acid-treated with hydrochloric acid, nitric acid, sulfuric acid and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) _{3 and the} like are preferably subjected to salt treatment. In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a block copolymer having excellent particle properties. The above components are usually used after being dehydrated and dried.

C. [C] Organoaluminum Compound An example of an organoaluminum compound used as the [C] component of the present invention is represented by the following formula: AlR _m X _3-m
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, aryloxy group, m is a number of 0 <m ≦ 3), specifically Is a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum or a halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum ethoxide. In addition, aluminoxane such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferred. These [C] components may be used in combination of two or more. In addition, a [C] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

D. Contact and Support The above [A] component, [B] component, and [C] component are brought into contact with each other to form a catalyst, but the contact method is not particularly limited. This contact may be performed not only during catalyst preparation but also during prepolymerization with olefins or during polymerization of olefins. A polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or alumina may be allowed to coexist or contact with each other when the catalyst components are contacted or after contact.
The contact may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene. The contact temperature is between −20 ° C. and the solvent boiling point, and particularly preferably between room temperature and the solvent boiling point.

E. Use amount of catalyst component The use amount of each component of the catalyst is, for example, 0.0001 to 10 mmol, preferably 0.001 to 5 mmol of [A] component per 1 g of component (B-3), and 0 of [C] component. 0.001 to 10,000 mmol, preferably 0.01 to 100 mmol. Moreover, the atomic ratio of the transition metal in the [A] component and the aluminum in the [C] component is 1: 0.01 to 1,000,000, preferably 0.1 to 100,000. The catalyst thus obtained may be used without washing as it is, or may be used after washing.
You may use it combining a [C] component newly as needed. The amount of the [C] component used at this time is selected so that the atomic ratio of aluminum in the [C] component to the transition metal in the [A] component is 1: 0 to 10,000.

F. Prepolymerization Prior to polymerization, olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene are preliminarily prepared. A polymerized polymer and washed as necessary can be used as a catalyst. This prepolymerization may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene.

(2) Aspects of production method The block copolymer of the present invention comprises at least three components, and as a production method thereof, a method by melt kneading or a method by a multistage polymerization method having three or more stages should be adopted. Can do.
From the viewpoint of improving the impact resistance of the block copolymer, it is preferably produced by a multistage polymerization method having three or more stages.
The amount ratio of each component can be controlled by adjusting the polymerization conditions of the multistage polymerization and selecting the blend components.

(2-1) Melt-kneading (blending) method In the case of producing by melt-kneading, for example, in the case of three components, the components (a), (b-1), (b-2) themselves are separately polymerized, and the predetermined Or a block copolymer produced by multistage polymerization of component (a) and component (b-1) and component (a) and component (b-2) in multiple stages Random block copolymer produced by mixing a block copolymer produced by polymerization at a predetermined ratio and then melt-kneading it, or by multi-stage polymerization of component (b-1) and component (b-2) A method in which the component (a) is mixed at a predetermined ratio and then melt-kneaded for production can be employed.
When manufacturing by melt kneading, a technique of melt kneading with a single or twin screw extruder or a brabender is employed.

When each of the above components (a), (b-1), and (b-2) is polymerized separately, the polymerization process for producing each component is carried out using a slurry method, a bulk method, a gas method for each component. Although a phase method, a solution method, etc. can be used arbitrarily, in the production of the component (a), the bulk method or the gas phase method is most preferably used, and the components (b-1) and (b-2) Regarding production, since these components are so-called elastomers, the solution method is most preferably used from the viewpoint of easy recovery of the finally obtained polymer. As the polymerization method, either a batch polymerization method or a continuous polymerization method can be employed.
The polymerization temperature can be used without any particular problem as long as it is in a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., preferably 40 ° C. to 100 ° C. can be used. Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 and 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, it is possible to coexist an inert gas such as nitrogen.

Moreover, the block copolymer which manufactured the component (a) and the component (b-1) by multistage polymerization, and the block copolymer which manufactured the component (a) and the component (b-2) by multistage polymerization in a predetermined ratio. When mixing and melt-kneading, each block copolymer is produced by producing the component (a) at the first stage and producing the component (b-1) or the component (b-2) at the second stage. It can manufacture by performing multistage polymerization. In this case, the slurry process, bulk method, gas phase method, solution method, etc. can be arbitrarily used as the polymerization process. Furthermore, a separate polymerization process is adopted for each of the first stage and the second stage. Also good. Among them, the production of the first stage component (a) is most preferably carried out by the bulk method or the gas phase method, and the production of the second step component (b-1) or the component (b-2) is carried out by the gas phase method. . As a polymerization method, either a batch polymerization method or a continuous polymerization method can be employed.
The polymerization temperature can be used without any particular problem as long as it is in a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., preferably 40 ° C. to 100 ° C. can be used. Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 and 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, it is possible to coexist an inert gas such as nitrogen.

(2-2) Three-stage polymerization (multi-stage polymerization) method i) Three-stage polymerization As a method for producing the composition of the present invention, component (a) is produced in the first stage, and component (b- It is also possible to employ a three-stage polymerization method in which 1) is produced and component (b-2) is produced in the third stage. As the polymerization process in this case, a slurry method, a bulk method, a gas phase method, a solution method, or the like can be arbitrarily used. Most preferably, the production of the second-stage component (b-1) and the third-stage component (b-2) is carried out by a gas phase method. As a polymerization method, either a batch polymerization method or a continuous polymerization method can be employed.
The polymerization temperature can be used without any particular problem as long as it is in a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., preferably 40 ° C. to 100 ° C. can be used. Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 and 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, it is possible to coexist an inert gas such as nitrogen. Moreover, about the component ratio of each component (a), (b-1), (b-2), it can adjust by controlling the manufacturing-amount ratio of each component.

ii) Measurement of characteristic value (index) The ethylene content and molecular weight index of each component when manufactured by multi-stage polymerization of three or more stages are sequentially analyzed by the TREF-GPC-IR method after completion of each stage of polymerization. Thus, the ethylene content and molecular weight of the polymer polymerized at each stage can be determined. In this case, the index of the copolymer manufactured in the third and subsequent stages is calculated by taking into account the index of the copolymer manufactured in the previous stage.
For example, the analysis of the copolymer component in the case of three-stage polymerization in which components (a), (b-1), and (b-2) are polymerized in this order is performed at the end of polymerization of component (a) and component (b-1). At the end of the polymerization until (b), the polymerization amount, the ethylene content and the molecular weight are measured for the sample subjected to the polymerization until (b-2), and the index of each component is determined.

In particular, the component (b-2) can be calculated according to the following formulas (IV) and (V).
Mw (b) = W (b−1) × Mw (b−1) + W (b−2) × Mw (b−2) (IV)
[E] (b) = W (b−1) × [E] (b−1) + W (b−2) × [E] (b−2) (V)
Here, Mw (b) and [E] (b) are the weights of copolymer components (mixture of component (b-1) and component (b-2)) determined from the analysis at the end of the third stage polymerization, respectively. The average molecular weight and the ethylene content. Mw (b-1) and [E] (b-1) are the weight average molecular weight and the ethylene content of the component (b-1) obtained from the analysis at the end of the second stage polymerization, respectively. is there.
The amount of polymerization can be determined by disconnecting the reactor from the polymerization system at the end of each stage and directly measuring the amount of polymer in the reactor as it is. Alternatively, there is a technique for determining the polymerization amount by separately polymerizing only the component (a) and two-stage polymerization of the component (a) and the component (b-1) under the same conditions as the multistage polymerization. In the case of four or more stages of polymerization, it can be calculated by extending these equations.

In the case of analyzing with an extracted sample, the amount of polymerization, the average molecular weight and the average ethylene content in each stage are measured without fractionation by TREF, and the index of each component is also obtained using the above formula. You can also. In that case, the following formulas (VI) to (IX) are used.
Mw [(a) + (b-1)] = [W (a) * Mw (a) + W (b-1) * Mw (b-1)] / [W (a) + W (b-1)] ... (VI)
Mw (total) = [W (a) + W (b-1)] × [Mw (a) + Mw (b-1)] + [W (b-2) × Mw (b-2)] ( VII)
[E] [(a) + (b-1)] = [W (a) * [E] (a) + W (b-1) * [E] (b-1)] / [W (a) + W (b-1)] (VIII)
[E] (total) = [W (a) + W (b-1)] * [E] [(a) + (b-1)] + [W (b-2) * [E] (b-2 )] ... (IX)
Here, Mw (a), Mw (b-1), and Mw (b-2) are the weight average molecular weights of the component (a), the component (b-1), and the component (b-2), respectively. Mw [(a) + (b-1)] is the weight average molecular weight of the sample polymerized to component (b-1), and Mw (total) is the sample polymerized to component (b-2). It is a weight average molecular weight and can be evaluated by GPC measurement of an extracted sample. Similarly, [E] (a), [E] (b-1), and [E] (b-2) are the ethylene contents of component (a), component (b-1), and component (b-2), respectively. is there. [E] [(a) + (b-1)] is the ethylene content of the sample polymerized up to component (b-1), and [E] (total) is polymerized up to component (b-2). It is the ethylene content of the sample and can be evaluated by IR measurement of the extracted sample. W (a), W (b-1), and W (b-2) are the weight fractions of component (a), component (b-1), and component (b-2), respectively. In the case of four or more stages of polymerization, it can be calculated by extending these equations.

3. Others (1) Use of Additives In order to enhance the performance of the composition of the present invention or to impart other performance to the resin composition of the present invention, the functions of the present invention are not impaired. Additives can also be blended.
As this additional component, a nucleating agent widely used as a compounding agent for polyolefin resin, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a neutralizer, a light stabilizer, an ultraviolet absorber, a lubricant Various additives such as antistatic agents, metal deactivators, peroxides, fillers, antibacterial agents, antifungal agents, fluorescent whitening agents, and coloring agents can be added. In addition, a rubber material can be added to further improve the impact resistance.
The amount of these additives is generally 0.0001 to 3 parts by weight, preferably 0.001 to 1 part by weight, based on 100 parts by weight of the composition. Further, various rubbers for improving impact resistance are generally added in an amount of 1 to 70 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the composition.

Here, as examples of rubber for improving impact resistance, ethylene / α-olefin elastomers and styrene elastomers are preferably used. Examples of the comonomer copolymerized with ethylene in the ethylene / α-olefin elastomer include α-olefins having 4 to 20 carbon atoms, specifically 1-octene, 1-butene and the like. It may be a mixture of two or more ethylene / α-olefin elastomers or styrene elastomers. The content of the α-olefin in the ethylene / α-olefin elastomer is 10 to 60% by weight, preferably 20 to 50% by weight, and the density is 0.85 to 0.90 g / cm ³ , preferably 0.86 to 0%. .88 g / cm ³ .
The styrene elastomer is a block or random copolymer of styrene and ethylene, propylene, 1-butene, butadiene, isoprene or the like, or a hydrogenated product thereof. The amount of bound styrene in the styrene elastomer is 5 to 45. wt%, and preferably 10 to 40 wt%, the density of 0.88~0.95g / cm ^3, preferably 0.89~0.92g / cm ^3.
The MFR is 0.1 to 20 g / 10 min, preferably 0.5 to 10 g / 10 min. If the MFR is less than 0.1 g / min, the moldability and paintability are poor, and if the MFR exceeds 20 g / 10 min, the impact resistance is inferior. Here, MFR is a value measured under conditions of a die shape diameter of 2.095 mm and a length of 8.00 mm at 230 ° C. and a load of 2.160 kg.
The ethylene / α-olefin-based elastomer can be produced by polymerization using a known titanium-based catalyst or metallocene catalyst. In the case of a styrene-based elastomer, it can be obtained by a usual anionic polymerization method and its polymer hydrogenation technique.

(2) Applications Since the resin composition of the present invention has sufficiently improved rigidity, heat resistance, and impact resistance in a well-balanced manner, various kinds of packaging materials such as interior materials for vehicles such as automobiles and electrical products are used. It is useful as an industrial material. In particular, since the impact resistance at low temperatures (about −30 ° C.) has been improved, it is also effectively used as packaging materials for storage of frozen foods, containers thereof, and industrial materials for low temperatures.

In order to describe the present invention more specifically, preferred examples and comparative examples corresponding thereto are described below. The contrast between each example and each comparative example demonstrates the rationality and significance of the requirements of the configuration of the present invention, and further demonstrates the superiority of the present invention over the prior art.

In the following Examples and Comparative Examples, methods for measuring various physical properties, methods for producing the compositions, methods for evaluating the compositions, and methods for producing the components used are as follows.
1) TREF
This is described in paragraphs 0025-0028. 2) GPC
Apparatus: Waters GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Column: Showa Denko AD806M / S (3) Mobile phase solvent: Orthodox Chlorobenzene (ODCB) Measurement temperature: 140 ° C. Flow rate: 1.0 ml / min Injection volume: 0.2 ml Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) And dissolve at 140 ° C. for about 1 hour.
Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000 A solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL To create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method. Other details are described in paragraph 0030. 3) DSC
Measurements were made using a Seiko DSC. Other details are described in paragraph 0022.
4) DMA
The sample used was cut out from a 2 mm thick sheet formed by injection molding into a strip shape of 10 mm width × 18 mm length × 2 mm thickness. (See paragraph 0094 for injection molding. The same applies to the following test items.)
The apparatus uses ARES manufactured by Rheometric Scientific and has a frequency of 1 Hz. The measurement temperature was raised stepwise from −80 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
5) MFR
According to JIS K7210A method and condition M, measurement was performed under the following conditions.
Test temperature: 230 ° C. Nominal load: 2.16 kg Die shape: Diameter 2.095 mm Length 8.000 mm
6) Determination of ethylene content The average ethylene content in the copolymer was determined using an infrared spectrophotometer. The measurement conditions are shown below. Apparatus: Shimadzu FTIR-8300 Resolution: 4.0 cm ⁻¹ Measurement range: 4,000 to 400 cm ⁻¹ Sample adjustment: Polymer powder or pellets are adjusted to a film with a thickness of 500 μm by a heating and pressing press (temperature 190 ° C. preheating) Pressurized to 100 MPa after 2 minutes) Data processing: i) Using 760,700 cm ^-1 as a base point, calculate the absorbance peak area in that range. (Corresponds to ethylene content) ii) Calculate peak area / sample thickness. iii) A calibration curve is prepared with a sample whose ethylene content has been quantified in advance by NMR, and the ethylene content is quantified by the formula [ethylene content∝peak area / sample thickness].
7) Flexural properties Flexural elasticity The flexural modulus of the obtained composition was evaluated under the following conditions.
Standard number: Compliant with JIS K-7171 (ISO178) Testing machine: Precision universal testing machine Autograph AG-20kNG (manufactured by Shimadzu Corporation) Test specimen sampling direction: Flow direction Test specimen shape: Thickness 4 mm Width 10 mm Length 80 mm Test How to make pieces: Injection molding Condition adjustment: Leave in a temperature-controlled room adjusted to room temperature 23 ° C and humidity 50% for more than 24 hours Test room: Temperature-controlled room temperature adjusted to 23 ° C and humidity 50% Number of test pieces: 5 Distance between fulcrums: 32.0 mm Test speed: 1.0 mm / min
8) Impact strength Impact resistance was evaluated by Charpy impact test.
Standard number: Compliant with JIS K-7111 (ISO 179 / 1eA) Tester: Toyo Seiki Co., Ltd. Fully automatic Charpy impact tester (with constant temperature bath) Shape of test piece: Test piece with single notch (thickness 4 mm, width 10 mm, length) 80mm) Notch shape: Type A notch (notch radius 0.25mm) Impact speed: 2.9m / s Nominal pendulum energy: 4J Test piece preparation method: Cutting a notch into an injection-molded test piece (ISO 2818 compliant) Condition adjustment : Room temperature 23 ° C / humidity controlled at 50% humidity for 24 hours or longer Test room: Room temperature 23 ° C / humidity adjusted at 50% humidity Number of specimens: n = 5 Test temperature: 23 ° C, 0 ° C , -30 ° C (In the case of 0 ° C and -30 ° C, the test was performed after adjusting the condition for 40 minutes or more in a state where the thermostat was within ± 1 ° C of the test temperature) Energy 9) Heat resistance Heat resistance was evaluated by heat distortion temperature (HDT). HDT was measured flat-wise under the condition of 0.45 MPa in accordance with JIS K7191-1 using an injection-molded piece having a thickness of 4 mm. However, as the test piece state adjustment before measurement, after injection molding, an operation of annealing at 100 ° C. for 30 minutes and cooling to room temperature is performed.

[Production Example 1] Three-stage polymerization Example 1) Preparation of component [A] (r) -dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H -Azurenyl}] synthesis of hafnium (synthesis of racemic meso mixture);
2-Fluoro-4-bromobiphenyl (6.35 g, 25.3 mmol) was dissolved in a mixed solvent of diethyl ether (50 mL) and hexane (50 mL), and a pentane solution of t-butyllithium (33 mL, 50.6 mmol, 1. 54N) was added dropwise at -78 ° C. The mixture was stirred at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. Hexane (30 mL × 2) was added and the supernatant was decanted. Hexane (30 mL) and tetrahydrofuran (40 mL) were added to the obtained yellow precipitate at 0 ° C. N-methylimidazole (50 μL) and dimethyldichlorosilane (1.4 mL, 11.4 mmol) were added, and the mixture was warmed to room temperature and stirred at room temperature for 1 hour. After this, dilute hydrochloric acid was added and the layers were separated, and then the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -1 , 4-dihydroazulene} was obtained (8.3 g).
Next, the crude product obtained above was dissolved in diethyl ether (30 mL), and a hexane solution of n-butyllithium (14.9 mL, 22.8 mmol, 1.53N) was added dropwise at -70 ° C. The mixture was warmed and stirred overnight at room temperature. Furthermore, toluene (200 mL) was added, and the mixture was cooled to −70 ° C., hafnium tetrachloride (3.6 g, 11.4 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 4 hours. Most of the solvent was removed from the resulting slurry solution under reduced pressure, diethyl ether (50 mL) was added, and the resulting slurry was filtered. After washing with diethyl ether (5 mL × 2), ethanol (15 mL × 2), hexane (10 mL × 2), dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) ) -4H-azulenyl}] hafnium racemic meso mixture (4.53 g, 42% yield) was obtained.

Purification of racemate: The racemic / meso mixture (4.5 g) obtained above was suspended in dichloromethane (35 mL) and irradiated with light using a high pressure mercury lamp (100 W) for 1 hour. The solvent was distilled off from this solution under reduced pressure. Toluene (25 mL) and dichloromethane (11 mL) were added to the obtained solid and heated to 60 ° C. to obtain a homogeneous solution. When dichloromethane was distilled off from this under reduced pressure, crystals were precipitated and filtered. After washing with hexane (5 mL × 2) and drying under reduced pressure, a racemate (1.79 g, 37%) was obtained.
1H-NMR (300 MHz, CDCl ₃ ); δ 1.02 (s, 6H, SiMe ₂ ), 1.08 (t, J = 8 Hz, 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, 2H, 4-H), 5.85-6.10 (m, 8H ), 6.83 (d, J = 12 Hz, 2H), 7.30-7.6 (m, 16H, arom)

2) Preparation of component [B] [Chemical treatment] Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 500 g of ion-exchanged water was added, and 249 g (5.93 mol) of lithium hydroxide monohydrate was further added. 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, a part of the sulfuric acid is consumed in the neutralization reaction to form a lithium sulfate salt in the system, and when the sulfuric acid becomes excessive, it becomes an acidic solution. Further, 350 g of commercially available granulated montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL average particle size: 28.0 μm) is added and stirred. Thereafter, the temperature is raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. The slurry was filtered under reduced pressure using a device in which an aspirator was connected to Nutsche and a suction bottle. The cake was collected, 5.0 L of pure water was added to reslurry, and filtration was performed. This operation was repeated four more times.
All filtrations were completed in less than a few minutes. The pH of the final washing liquid (filtrate) was 5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. As a result, 275 g of a chemically treated product was obtained. As a result of compositional analysis by fluorescent X-ray, the molar ratio of the constituent elements to silicon as the main component was Al / Si = 0.21, Mg / Si = 0.046, and Fe / Si = 0.022. .
[Organic Aluminum Treatment of Chemically Treated Montmorillonite] 10.0 g of the chemically treated montmorillonite obtained above was weighed into a 1 L flask, and 64.6 ml of heptane and 35.4 ml (25 mmol) of a heptane solution of triisobutylaluminum were added. For 1 hour. Thereafter, it was washed with heptane, and finally the amount of slurry was adjusted to 100 ml.

3) Prepolymerization with Propylene 2.13 ml (1504 μmol) of a triisobutylaluminum heptane solution was added to the triisobutylaluminum-treated montmorillonite heptane slurry prepared above and stirred for 10 minutes at room temperature. In another flask (volume 200 mL), (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl] synthesized above was used. }] After adding toluene (60 ml) to hafnium (299 μmol) to form a slurry, the slurry was added to the 1 L flask and stirred at room temperature for 60 minutes.
The toluene slurry of the complex was analyzed and the dissolved component and the insoluble component of the complex were determined. The dissolved component of the complex was 60 μmol, the insoluble component was 239 μmol, and the dissolved component was 6 μmol / g-carrier for montmorillonite. there were.
Next, 340 ml of heptane was further added to the above montmorillonite heptane slurry, and the mixture was introduced into a stirring autoclave having an internal volume of 1 L and stirred for 60 minutes. After the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at a constant rate of 238.1 mmol / hr (10 g / hr) for 120 minutes. After the completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The total time required for the prepolymerization was 4 hours. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 31.8 g of a solid catalyst. The pre-polymerization magnification (the value obtained by dividing the pre-polymerized polymer amount by the solid catalyst amount) was 2.09.

4) Polymerization Polymerization comprising the following first to third steps was carried out to produce a propylene-ethylene block copolymer.
(Polymerization in the first step) After the inside of the autoclave with a stirrer having an internal volume of 3 L was sufficiently substituted with propylene, 2.76 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, followed by 700 ml of hydrogen, followed by liquid propylene 1, 500 ml was introduced and the temperature was raised to 65 ° C. The prepolymerized catalyst obtained in the above 3) was slurried with heptane, and 40 mg (amount of net solid catalyst excluding prepolymerized polymer) was injected as a solid catalyst to initiate polymerization. The tank temperature was maintained at 65 ° C. After 1 hour from the addition of the catalyst, the remaining monomer was purged and completely replaced with purified nitrogen. A part of the produced polymer was sampled and measured after drying for 30 minutes under a nitrogen stream at 90 ° C. As a result, the extraction amount was 15 g.
(Polymerization in the second step) In parallel, a mixed gas tank of propylene and ethylene (autoclave with a stirrer having an internal volume of 14 L) was mixed with 72.49 vol% of propylene, 27.49 vol% of ethylene and 0.02 vol% of hydrogen. The gas was prepared at 80 ° C. and 2.7 MPa gauge pressure. After the stirring of the polymerization tank was resumed and the inside of the polymerization tank was adjusted to an internal pressure of 1.5 MPa gauge pressure with a gas composition of 43 vol% propylene and 57 vol% ethylene, the pressure of the polymerization tank was adjusted to 1.5 MPa gauge. The gas phase copolymerization of propylene / ethylene was performed at 65 ° C. for 5 minutes. Thereafter, the residual monomer was purged, and a part of the produced polymer was sampled and measured after drying for 30 minutes under a nitrogen stream at 90 ° C. As a result, the amount extracted was 15 g.
(Polymerization in the third step) In parallel, a mixed gas tank of propylene and ethylene (autoclave with a stirrer with an internal volume of 14 L) was mixed with 44.99 vol% of propylene, 54.98 vol% of ethylene and 0.03 vol% of hydrogen. The gas was prepared at 80 ° C. and 2.7 MPa gauge pressure. After the stirring of the polymerization tank was resumed and the inside of the polymerization tank was adjusted to a 2.0 MPa gauge pressure with a gas composition of 24 vol% propylene and 76 vol% ethylene, the pressure of the polymerization tank was adjusted to 2. Supply was performed so that the pressure was 0 MPa gauge, and vapor phase copolymerization of propylene / ethylene was performed at 80 ° C. for 20 minutes. The polymer recovered after the polymerization was dried for 30 minutes under a nitrogen stream at 90 ° C.
The polymerization conditions are summarized in Table 1a. A small sample is taken out at each stage of the polymerization, and the ethylene content and molecular weight measurement results are shown in Table 1a. Table 1b shows the analysis results of the extracted samples by the TREF-GPC-IR method.

[Production Example 2] Three-stage polymerization example A block copolymer was produced in the same manner as in Production Example 1 except that the polymerization conditions were changed as shown in Table 1a. Moreover, a small sample was extracted at each stage of the polymerization, and the results of ethylene content and molecular weight measurement are shown together in Table 1a. Table 1b shows the analysis results of the extracted samples by the TREF-GPC-IR method.

[Production Example 3] Composition production example of kneading component (a) and component (b-1) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 82 vol% propylene and 18 vol% ethylene, and other polymerization conditions were as shown in Table 2.
For Production Example 3, since the ethylene content in the second stage polymerization was too low and fractionation by TREF was insufficient, the amount of copolymer component and The ethylene content was determined. As a result, the propylene polymer part Mw was 1.20 × 10 ⁵ , the copolymer part Mw was 3.88 × 10 ⁵ , the copolymer component content was 20.0 wt%, and the copolymer part ethylene content was 5 0.0 wt%.
Each production example shown above was repeated several times if necessary to produce a required amount of polymer and used in the following examples.

[Production Example 4] Composition production example of kneading component (a) and component (b-1) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was changed to propylene 54 vol%, ethylene 46 vol%, and other polymerization conditions as described in Table 2.
The results obtained by analyzing the samples obtained in these production examples by the TREF-GPC-IR method are also shown in Table 2. Each production example shown above was repeated several times if necessary to produce a required amount of polymer and used in the following examples.
Similarly, in each of the following production examples, the results obtained by analyzing the obtained samples by the TREF-GPC-IR method are shown together in Table 2, and each production example is repeated several times if necessary to obtain the required amount of polymer. And was used in the following examples.

[Production Example 5] Composition production example of component (a) for kneading and component (b-1) A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was changed to 42 vol% propylene and 58 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 6] Composition production example of kneading component (a) and component (b-1) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was changed to 28 vol% propylene and 72 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 7] Composition production example of kneading component (a) and component (b-1) A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was changed to 42 vol% propylene and 58 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 8] Composition production example of kneading component (a) and component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was changed to 28 vol% propylene and 72 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 9] Composition production example of kneading component (a) and component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 24 vol% propylene and 76 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 10] Composition production example of kneading component (a) and component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 21 vol% propylene and 79 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 11] Composition Production Example of Component (a) for Kneading and Component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 16 vol% propylene and 84 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 12] Composition production example of kneading component (a) and component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 24 vol% propylene and 76 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[Production Example 13] Composition production example of kneading component (a) and component (b-2) A block copolymer was produced by two-stage polymerization. Manufactured in the same manner as in Production Example 1 except that the gas composition in the polymerization tank in the second step was 24 vol% propylene and 76 vol% ethylene, and other polymerization conditions were as shown in Table 2.

[Production Example 14] Production example using Ziegler catalyst (preparation of solid catalyst component) 2,000 mL of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 2.6 mol of MgCl ₂ and Ti 5.2 mol of (OnC ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 320 mL of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Next, 4,000 mL of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 2.62 mol of SiCl ₄ was mixed with 25 mL of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.15 mol of phthalic acid chloride was mixed with 25 mL of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (A1) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0 wt%.
Subsequently, 200 mL of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 4 g of the solid component (A1) synthesized above was introduced, 0.035 mol of SiCl ₄ was introduced, and 90 ° C. was introduced. The reaction was performed for 2 hours. After completion of the reaction, further (CH ₂ = CH) Si (CH ₃ ) ₃ 0.006 mol, (t-C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ 0.003 mol and Al (C ₂ H ₅ ) ₃ 0.016 mol was sequentially introduced and contacted at 30 ° C. for 2 hours. After completion of the contact, the solid catalyst component (A) mainly composed of magnesium chloride was obtained by thoroughly washing with n-heptane. When a part was sampled and analyzed, the titanium content of the sample was 1.8 wt%.
(The above catalyst preparation was carried out by the method described in Example 1 of JP-A-11-80235.)
(Preparation of Preliminary Polymerization Catalyst) Purified n-heptane was introduced into the solid catalyst component (A) to adjust the concentration of the solid catalyst component (A) to 20 g / L. After cooling the slurry to 15 ° C., _Al a _{(C 2} H _{5) 3} of n- heptane diluent 0.5g was added as _{Al (C 2} H _{5) 3,} was fed slowly propylene 9g. After the supply of propylene was completed, the reaction was continued for another 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain a prepolymerized catalyst (B). This prepolymerized catalyst (B) contained 2.0 g of polypropylene per 1 g of the solid catalyst component (A).

(Production of propylene ethylene block copolymer) Polymerization in the first step: After sufficiently replacing an autoclave having an internal volume of 3 L with stirring and a temperature control device with propylene, 4.82 mol of triethylaluminum was diluted with n-heptane and added. 5,500 ml of hydrogen and then 750 g of liquid propylene were introduced, and the temperature was raised to 70 ° C. to maintain the temperature. The prepolymerized catalyst (B) was slurried with n-heptane, and 7 mg (excluding the weight of the prepolymerized polymer) was injected as a catalyst to initiate polymerization. Polymerization was continued for 40 minutes while maintaining the temperature in the tank at 70 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. A part of the produced polymer was sampled and sufficiently dried and used for analysis.
Second step polymerization: Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 80 ° C., and the mixed gas composition was ethylene 29.70 vol%, propylene 69.07 vol%, and hydrogen 1.23 vol%. After a part of the polymer was sampled in the first step, this mixed gas was supplied to a 3 L autoclave to start polymerization in the second step. The polymerization was continued at a polymerization temperature of 80 ° C. and a pressure of 2.0 MPaG for 17 minutes. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization. The recovered polymer was sufficiently dried in an oven.
Table 2 shows the results of analyzing the obtained sample by the TREF-GPC-IR method.

[Example 1]
The following antioxidant and neutralizer were added to the polymer powder obtained in Production Example 1 and mixed thoroughly with stirring. (Additive composition) Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm Tris (2,4-di-t-butylphenyl) ) Phosphite 500ppm Neutralizer: Calcium stearate 500ppm
The physical properties of the product granulated and molded under the following conditions were evaluated. The granulation conditions and molding conditions are shown below.
(Granulation) Extruder: Technobel KZW-15-45MG twin screw extruder Screw: 15 mm caliber L / D = 45 Extruder set temperature: (from under hopper) 40, 80, 160, 200, 200, 200 (die ℃) Screw rotation speed: 400rpm Discharge amount: Adjusted to about 1.5kg / hr with screw feeder Die: 3mm diameter Strand die 2 holes
(Molding) The obtained raw material pellets were injection molded under the following conditions to obtain flat plate test pieces for evaluating physical properties. Standard number: JIS K-7152 (ISO 294-1) Reference molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co., Ltd. Molding machine set temperature: (from under the hopper) 80, 210, 210, 200, 200 ° C. Mold temperature: 40 ° C Injection speed: 52 mm / s (screw speed) Holding pressure: 30 MPa Holding pressure time: 8 seconds Mold shape: flat plate (thickness 4 mm, width 10 mm, length 80 mm) 2 index Resin composition index, TREF-GPC- Table 3 shows analysis data and physical property data by IR. The following examples are also shown in Table 3.

[Example 2]
The same procedure as in Example 1 was performed except that the powder obtained in Production Example 2 was used.
[Example 3]
The same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 20:80 as the block copolymer. It was. At this time, the copolymer component of Production Example 5 can be regarded as the compatibilizer component (b-1), and the copolymer component of Production Example 9 can be regarded as the copolymer component (b-2).
[Example 4]
The same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 4 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 20:80 as the block copolymer. It was.
[Example 5]
The same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 10 were mixed at a weight ratio of 20:80 as the block copolymer. It was.
[Example 6]
The same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 35:65 as the block copolymer. It was.
[Example 7]
The same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 5:95 as the block copolymer. It was.
[ Reference example ]
As the block copolymer, the same procedure as in Example 1 was performed except that the block copolymer powder of Production Example 7 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 20:80. It was.

[Comparative Example 1] The same operation as in Example 1 was conducted except that the block copolymer powder of Production Example 9 was used alone as the block copolymer. Table 4 shows the index of the resin composition, analysis data by TREF-GPC-IR, and physical property data. The following comparative examples are also shown in Table 4.
[Comparative Example 2] The same procedure as in Example 1 was conducted except that the block copolymer powder of Production Example 13 was used alone as the block copolymer.
[Comparative Example 3] Example except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 50:50 as the block copolymer. 1 was performed.
[Comparative Example 4] Example except that the block copolymer powder of Production Example 3 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 20:80 as the block copolymer. 1 was performed.
[Comparative Example 5] Example except that the block copolymer powder of Production Example 6 and the block copolymer powder of Production Example 9 were mixed at a weight ratio of 20:80 as the block copolymer. 1 was performed.
[Comparative Example 6] Example except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 8 were mixed at a weight ratio of 20:80 as the block copolymer. 1 was performed.
[Comparative Example 7] Example except that the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 11 were mixed at a weight ratio of 20:80 as the block copolymer. 1 was performed.
[Comparative Example 8] Example except that the block copolymer powder of Production Example 7 and the block copolymer powder of Production Example 12 were mixed at a weight ratio of 20:80 as the block copolymer. 1 was performed.
[Comparative Example 9] The procedure of Example 1 was repeated except that the block copolymer powder of Production Example 14 was used alone as the block copolymer.

[Example 9] As a block copolymer, a mixture of the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 in a weight ratio of 20:80 was made 100 parts by weight, and The same procedure as in Example 1 was performed except that 20 parts by weight of EOR-1: (ethylene / octene rubber: DuPont Dow-ENGAGE8100: MFR = 2.0 g / 10 min) was added. Table 5 shows the evaluation results of the physical properties.
[Example 10] As a block copolymer, a mixture of the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 in a weight ratio of 20:80 was made 100 parts by weight, and The same procedure as in Example 1 was carried out except that 20 parts by weight of SEBS-1 (styrene / ethylene / butene / styrene block polymer rubber: Clayton G2657: MFR = 9.0 g / 10 min, manufactured by Shell) was added. Table 5 shows the evaluation results of the physical properties.
[Example 11] As a block copolymer, a mixture of the block copolymer powder of Production Example 5 and the block copolymer powder of Production Example 9 in a weight ratio of 20:80 was made 100 parts by weight, and The same procedure as in Example 1 was conducted except that 20 parts by weight of EBM-1 (ethylene butene rubber: Tuffmer A1050S manufactured by Mitsui Chemicals, Inc .: MFR = 2.4 g / 10 min) was added. Table 5 shows the evaluation results of the physical properties.

[Consideration by contrast between Example and Comparative Example]
Considering each of the above Examples and Comparative Examples in comparison, the blending amount and ethylene content of the propylene polymer (a) component, the blending amount and ethylene content of the copolymer component (b) by TREF, and TREF A novel propylene-based resin satisfying the requirements in the essential constituent elements of the present invention, comprising the quantitative ratio of copolymer components (b-1) and (b-2), the respective ethylene contents, and the melting point of the composition In each example of the composition, it is clear that the balance between the flexural modulus, which is an index of rigidity, and the impact resistance at each temperature is very excellent.
Furthermore, in each Example, the impact resistance at a low temperature (−30 ° C.) is improved, and the copolymer component (b- Since 1) is blended under specific conditions, it can be seen that the impact resistance at each temperature also increases synergistically. In addition, the heat resistance is balanced with other physical properties, and each example of the present invention is superior in heat resistance in terms of rigidity as compared with Comparative Example 9 using a Ziegler catalyst. In particular, in Examples 9 to 11, since the elastomer component is additionally contained, the balance between rigidity and impact resistance is good, and the impact resistance at each temperature is also very good.
In Comparative Examples 1 and 2, since the component (b-1) having a low ethylene content as a compatibilizer component is not included, the impact strength at each temperature is inferior. Is good, but the impact resistance is poor and unbalanced. In Comparative Example 3, since the blending amount of (b-1) serving as a compatibilizing agent component is too large, the ethylene content of the component (b) as a whole is slightly lowered, and as a result, the impact strength at low temperatures is inferior. In Comparative Example 4, the ethylene content of the component (b-1) is too low and the compatibility with the component (b-2) is deteriorated. As a result, the impact resistance at each temperature is inferior. Moreover, as seen in Table 6, the glass transition temperature derived from the propylene polymer of Comparative Example 4 is slightly lower than that of the other examples, and the component (b-1) is preferentially compatible with the component (a). You can see that For this reason, the rigidity is somewhat inferior. On the contrary, in Comparative Example 5, the ethylene content of component (b-1) is too high, the compatibility with component (a) deteriorates, and the impact resistance at each temperature is also inferior. In Comparative Example 6, the ethylene content of component (b-2) is too low to sufficiently lower the glass transition temperature (tan δ peak temperature), and the impact resistance at low temperatures is poor. In Comparative Example 7, although the ethylene content of component (b-2) and the ethylene content of copolymer (b) were too high, the ethylene content range of component (b-1) was appropriate, Deterioration is inevitable, and impact resistance at each temperature is inferior. In Comparative Example 8, since the weight average molecular weight of component (b-2) is too low, the impact resistance at each temperature is inferior. Since Comparative Example 9 is a propylene-based resin composition produced by a conventional technique using a Ziegler-based catalyst, the glass transition temperature is higher compared to each Example, and the rigidity and impact resistance at low temperature are low. The balance is inferior.
From the results and discussions of the examples and comparative examples described above, the rationality and significance of the requirements of the configuration of the present invention are demonstrated, and the exceptional superiority of the present invention over the prior art is also clarified. ing.

Claims (5)

A propylene homopolymer component, or a crystalline propylene polymer component (a) composed of a copolymer of propylene and up to 3 wt% of ethylene or an α-olefin having 4 to 20 carbon atoms, and propylene-ethylene copolymer A propylene-based resin comprising a polymer component (b) of 40 to 5 wt%, wherein each component is polymerized using a metallocene catalyst and satisfies the following characteristics i) to iv) and vi), vii ) Composition.
i) The melting point obtained by differential scanning calorimetry (DSC) is 156 to 180 ° C.
ii) The proportion of the copolymer component (b) obtained from temperature-elevated solubility fractionation measurement (TREF) for fractionation at three levels of 40 ° C., 100 ° C., and 140 ° C. is 5 to 40 wt%.
iii) The ethylene content of the copolymer component (b) determined from temperature-elevated solubility fractionation measurement (TREF) for fractionation at three levels of 40 ° C., 100 ° C., and 140 ° C. is 30 to 50 wt%, The average ethylene content in the components eluted at ~ 100 ° C is 10 wt% or less.
iv) The propylene-ethylene copolymer component (b) comprises at least two types of propylene-ethylene copolymer components (b-1) and components (b-2) having different ethylene contents, and the component (b-1) The ethylene content is 15-30 wt%, the ethylene content of component (b-2) is 40-55 wt%, and the quantitative ratio (b-1) of component (b-1) and component (b-2): (b -2) is in the range of 1:99 to 40:60.
vi) Both the weight average molecular weights of the component (b-1) and the component (b-2) of the propylene-ethylene copolymer are 250,000 to 1,000,000, and the weight average molecular weight of the component (a) is 60 Must be from 50,000 to 250,000.
vii) The weight average molecular weight of the component (b-1) of the propylene-ethylene copolymer is not less than the weight average molecular weight of the component (b-2). The propylene-based resin composition according to claim 1, which satisfies the following characteristic v).
v) The peak temperature of tan δ derived from the propylene-ethylene copolymer component (b) obtained by solid viscoelasticity measurement at a frequency of 1 Hz in the range of -80 to 150 ° C is -47 ° C or lower. Each component is prepared by sequential multistage polymerization, or separately polymerized respective components are mixed, or characterized in that it is produced in combination with these steps, according to claim 1 or claim 2 Propylene-based resin composition. Components (a) and (b) react with (A) a transition metal compound represented by the following general formula [I], and (B) (B-1) an organoaluminum oxy compound and (B-2) a transition metal compound. And (B-3) an ion-exchange layered compound (including silicate) as an essential component, and (C) an organoaluminum compound as an optional component. The propylene-based resin composition according to any one of claims 1 to 3, wherein the propylene-based resin composition is produced in the presence of a metallocene-based catalyst.

(In the general formula [I], A ¹ and A ² represent a conjugated five-membered ring ligand (in the same compound, A ¹ and A ² may be the same or different), and The carbon of the conjugated five-membered ring that is not bonded may have a substituent, Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M is a periodic table 4 ~ Represents a metal atom selected from Group 6; X and Y are each independently a hydrogen atom, halogen atom, hydrocarbon group, amino group, halogenated hydrocarbon group, oxygen-containing hydrocarbon group bonded to M; , Nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group.) It contains 1 to 70 parts by weight of ethylene / α-olefin elastomer or styrene elastomer with respect to 100 parts by weight of the propylene resin composition according to any one of claims 1 to 4. Polyolefin resin composition.