JP4889314B2 - Propylene-based resin composition with excellent impact resistance - Google Patents

Description

  The present invention relates to a propylene-based resin composition having excellent impact resistance, and more specifically, a three-component propylene-based block copolymer comprising a specific crystalline propylene polymer component and two specific propylene-ethylene copolymer components. A propylene-based resin composition comprising, as a component, a propylene-based block copolymer polymerized by a Ziegler-based catalyst, an ethylene / α-olefin-based elastomer or a styrene-based elastomer, and an inorganic filler, using the combined composition as an impact modifier component In particular, the present invention relates to a novel resin composition having excellent impact resistance and appearance performance of a molded product, excellent rigidity and heat resistance, and improved impact resistance at low temperatures.

Propylene-based resin, which is heavily used as an industrial material, is extremely excellent in rigidity and heat resistance, but has relatively low impact resistance, which is important as a physical property, so a random copolymer of propylene and ethylene or polypropylene As a composition obtained by blending with a copolymer thereof, a technique for improving impact resistance has been often used.
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 can be used in many industrial fields such as automobile interior and exterior and packaging materials. Has been used in.

Such a propylene-ethylene block copolymer is usually produced industrially using a Ziegler-based catalyst, but the Ziegler-based catalyst generally has various active sites (so-called multisite), and has a molecular weight distribution. It is known that the comonomer composition distribution in the propylene-ethylene copolymer part is wide. Thus, the propylene-based resin produced using the Ziegler-based catalyst has a wide composition distribution, and thus is excellent in the appearance performance of the molded product, particularly in the flow mark.
However, in the case of such a propylene-ethylene copolymer having a wide composition distribution, the homogeneity of the copolymerization is low, and the copolymer has a propylene chain or ethylene chain 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 the low molecular weight component of the copolymer component being dissolved in the crystalline polypropylene component. It 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 generated, impact resistance is improved, and compatibility with the crystalline polypropylene component can be controlled, so that the above-mentioned problems related to 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 thought that it is necessary to control the compatibility of the coalescence component within an appropriate range. The compatibility problem between this polypropylene component and the copolymer component is the propylene-ethylene block produced with the conventional Ziegler-based catalyst. It has also been seen in copolymers, and a method for increasing the compatibility of these components by adding a polypropylene component and a compatibilizing agent component of the copolymer part has been known for a long time (Patent Documents 5 and 6). See).
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 problems described in paragraph 0003 are 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, in the same manner as the method using the Ziegler-based catalyst, a propylene-based copolymer containing a propylene-ethylene copolymer compatibilizer component using a metallocene-based catalyst and having an excellent balance of rigidity, heat resistance and impact resistance. An attempt has been made to produce a resin composition by at least three-stage polymerization (see Patent Document 10). In the above-described three-stage polymerization method using a Ziegler catalyst, a metallocene system is used instead of a Ziegler catalyst. A composition is produced using a catalyst, and only a wide range of component ratios and ethylene contents, as well as a wide range of intrinsic viscosities and MFR, are specified. Specifically, the balance between rigidity, heat resistance and impact resistance is specified. It is difficult to say that a production method for a propylene-based resin composition excellent in the above is disclosed.

Furthermore, as another method for improving the propylene-based resin, various elastomer components are also added to improve the impact resistance of the propylene-based resin, but the performance of the elastomer to be added later is fully exhibited. In the propylene-based resin, it is necessary to include a component that helps disperse the elastomer component and reinforces the interface, and the addition of such a component causes a decrease in heat resistance and rigidity.
In addition, in the propylene-based resin composition using a metallocene catalyst, an attempt has been made to obtain a propylene-based resin composition having an excellent balance of rigidity, impact resistance, and heat resistance by combining an elastomer and an inorganic filler. Thus, since the propylene-ethylene block copolymer having a narrow composition distribution produced by the metallocene catalyst is used as a base, the affinity between the crystalline polypropylene component and the propylene-ethylene copolymer component is reduced. Propylene-based resin composition that adversely affects the particle size and interfacial strength of polymer components (elastomer components), and provides satisfactory physical properties in the balance of rigidity, heat resistance and impact resistance even when an elastomer or inorganic filler is added Cannot be obtained (see Patent Documents 11 and 12).
Similarly, by combining a propylene block copolymer with a metallocene catalyst and a propylene block copolymer with an elastomer and a Ziegler catalyst, a propylene resin composition having a balance of rigidity, impact resistance and heat resistance is obtained. Although attempts have been made, use as an impact modifier to elicit the performance of elastomers has not been sufficiently studied, and the disclosed propylene block copolymer still has satisfactory rigidity and impact resistance. And the balance of heat resistance and good moldability have not been obtained (see Patent Document 13).

  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 catalysts and metallocene-based catalysts that are widely used in the production thereof. Even in the propylene-based copolymer or propylene-based resin composition to which an improved technique has been added, it cannot be said that the rigidity, heat resistance and impact resistance, and further, the molded appearance has been sufficiently improved and improved in a balanced manner, In addition, the impact resistance at low temperatures is not always satisfactory, and it should be said that a balanced and comprehensive improvement is 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) JP 10-1573 A (summary) JP 2003-147158 A (summary) Japanese Patent Laying-Open No. 2003-147157 (abstract, claim 4 and paragraph 0025)

  Considering the flow of technical improvement of the propylene-based resin material in the prior art outlined as the background art, there have been a great number of attempts to improve the rigidity, heat resistance and impact resistance in a well-balanced manner. In addition to improvements, the appearance of molded products has also been improved. Moreover, despite the strong demand to improve impact resistance at low temperatures, which is a recent strong demand, such propylene is still available. The development of the resin-based resin material is not sufficiently achieved. Thus, the present invention should solve the above-described improvement and improvement in the propylene-based resin material. It is to be an issue.

However, the present inventors have sufficiently improved the rigidity, heat resistance and impact resistance of the propylene-based resin material in a well-balanced manner, and further improved the impact resistance at low temperatures, which is a recent strong demand. Aiming at the use of propylene-based block copolymer composition as a basic material obtained by using a three-stage polymerization production method or blending method of propylene-based block copolymer, Polymerization conditions and blending ratio of each component of the composition, ethylene content, compatibility function in the compatibilizer component, various characteristic values such as molecular weight and glass transition temperature, and physical properties of the composition by combining these characteristic values We examined and considered various changes from various viewpoints in detail and tried to compare and verify by experiment.
As a result of these processes, in the three-stage polymerization of a propylene-based resin composition composed of a propylene-based polymer and a propylene-ethylene copolymer, etc., using the characteristics of the metallocene-based catalyst, It is essential to improve compatibilities by specifying the ethylene content, to identify each component by the TREF method (temperature-elevated solubility fractionation measurement method), to enhance the impact properties by devising the mixing ratio of each component and the ethylene content. By realizing this recognition, the rigidity, heat resistance and impact resistance can be sufficiently improved in a well-balanced manner, and the impact resistance at low temperatures has also been improved. Thus, the present invention has been created and has been filed as a prior invention (Japanese Patent Application No. 2005-275623).

The embodiment of the invention of the prior application is a copolymer component with crystalline polypropylene and ethylene having specific physical properties in a propylene resin composition by a three-stage polymerization method or a three-component blend utilizing the characteristics of a metallocene catalyst. And a compatibilizer component (a crystalline propylene polymer and a propylene-ethylene copolymer [sometimes referred to as an elastomer]) that improves the solubility of the compatibilizer component, which is a specific copolymer having a relatively low ethylene content ) In a specific quantity ratio, and by defining each component using the TREF method, the rigidity, heat resistance and impact resistance of the propylene resin material are improved in a well-balanced manner, and the resistance at low temperatures is improved. It was finally possible to achieve sufficient improvement in impact resistance.
The propylene-based resin composition of the invention of the prior application basically includes a propylene homopolymer component or a crystalline propylene polymer composed of a copolymer of propylene and a copolymer of propylene with up to 3 wt% ethylene or an α-olefin having 4 to 20 carbon atoms. It comprises a blending component (a) of 60 to 95% by weight and a propylene-ethylene copolymer component (b) of 40 to 5% by weight, each component is polymerized using a metallocene catalyst, and the component (b) is further at least The resin composition is composed of two components, the ratio of the two components and the ethylene content are specified, and the melting point obtained by differential scanning calorimetry (DSC) and the proportion of the copolymer component determined from TREF are specified.

  The inventors have further improved the rigidity, heat resistance and impact resistance of propylene-based resin materials in a well-balanced manner, and also improved the appearance of the molded product, and further improved the impact resistance at low temperatures. As a result, research related to the invention of the prior application was continued, and a propylene block copolymer polymerized by a Ziegler catalyst using the resin composition of the prior application as an impact modifier was mainly used. When selected as an ingredient and combined with an elastomer and an inorganic filler as additional ingredients, the propylene-based resin material is sufficiently improved in rigidity, heat resistance and impact resistance, and the appearance of the molded product is also improved. In particular, it has been found that the flow mark performance of molded products can be improved and the impact resistance at low temperatures can be improved, and the present invention using the prior invention is created. Led was.

  The present invention basically uses a propylene-based resin composition produced using a metallocene-based catalyst according to the invention of the prior application as an impact resistance modifier, and is a propylene-based block copolymer that is polymerized by a Ziegler-based catalyst. Is a novel resin composition comprising an elastomer and an inorganic filler (which may be optional components), and the substantial main essence of the invention is propylene comprising a propylene-based polymer and a propylene-ethylene copolymer. In the three-stage polymerization of a block copolymer or in a three-component composition using a plurality of propylene block copolymers (including multicomponent systems of four or more components), the characteristics of metallocene catalysts are utilized. , Improvement of compatibilities by specifying the blending ratio and ethylene content of each component of the propylene block copolymer composition, melting point by DSC and TREF technique Certain of the components due to temperature rise Solubility fractionation assay), such as exaltation impact properties by devising the mixing ratio and the ethylene content of each component, composed of important requirement.

Specifically, the present invention is a propylene-based resin composition containing the components (I) to (IV).
Component (I): a propylene homopolymer component, or a crystalline propylene polymer component (a) composed of a copolymer of propylene with up to 3 wt% ethylene or an α-olefin having 4 to 20 carbon atoms, and 60 to 95 wt% And propylene-ethylene copolymer component (b) 40 to 5 wt%, each component is polymerized using a metallocene catalyst and satisfies the following characteristics i) to iv) 10 ~ 30% by weight
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 (b-2) having different ethylene contents, and the component (b-1) ethylene The content is 15-30 wt%, the ethylene content of the component (b-2) is 40-55 wt%, and the weight ratio (b-1) / (b-) of the component (b-1) and the component (b-2) 2) is in the range of 1:99 to 40:60.
Component (II): MFR (230 ° C., 21.18 N load) is 15 to 200 g / 10 minutes, and 30 to 80% by weight of a propylene block copolymer polymerized using a Ziegler catalyst
Component (III): 10 to 40% by weight of ethylene / α-olefin elastomer or styrene elastomer
Ingredient (IV): Inorganic filler 0 to 50% by weight

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 in component (I), and used for polymerization. It is also specified by selection of the metallocene catalyst to be used.

The main feature of the present invention is that, in a propylene-based block copolymer composition by a three-stage polymerization method or a three-component blend method using characteristics of a metallocene-based catalyst, crystalline polypropylene having specific physical properties, ethylene and The impact resistance of a propylene block copolymer composition formed by combining a copolymer component with a compatibilizer component, which is a specific copolymer having a relatively low ethylene content, in a specific quantity ratio, etc. As a material, it is blended in a propylene block copolymer that is polymerized using a Ziegler catalyst, and further blended with an elastomer. The propylene resin composition has rigidity, heat resistance and impact resistance. The balance is sufficiently improved, the appearance of the molded product is also improved, and the impact resistance at low temperatures (about -30 ° C) is sufficiently improved. And it makes it possible to.
In the present invention, the propylene-based block copolymer composition itself as an impact modifier is not only excellent in rigidity, impact resistance and heat resistance, but also by combining this with an elastomer, By improving the dispersion of the elastomer and the interfacial strength, it is possible to improve the impact strength without reducing the rigidity. In addition, since the propylene block copolymer produced with the metallocene catalyst has a narrow composition distribution, the appearance performance of the molded product is slightly inferior. Therefore, the polypropylene block copolymer polymerized with the Ziegler catalyst as the base component is used. By using a polymer and combining an elastomer and an inorganic filler, impact resistance and the like of the propylene-based resin composition can be improved and the appearance performance of the molded body can be improved.

Furthermore, in the present invention, as clarified from the comparison between each example and each comparative example, the impact resistance is improved by characterization of the mixing ratio of the two components of the specific propylene-ethylene copolymer. It is also a remarkable feature that it is increased synergistically.
In addition, in the propylene block copolymer composition by three-stage polymerization of a Ziegler catalyst, impact resistance increases as the blending ratio of the propylene-ethylene copolymer increases. In the present invention, a combination of a specific two-component propylene-ethylene copolymer is used, so that the combination of the two-component propylene-ethylene copolymer is used. It is possible to find a characteristic that impact resistance increases specifically. This characteristic is presumed to be due to the very high compatibility of the two components of the so-called rubber-like (elastomer) copolymer and the good affinity at the interface.

By the way, regarding the propylene-based block copolymer composition containing a compatibilizer, such as three-stage polymerization using a metallocene catalyst, which is one of the basic requirements of the present invention, paragraphs in the background art above Examining each of the patent documents described in 0010 and other prior art patent documents, Patent Document 1 (Japanese Patent Application Laid-Open No. H8-67883) is a metallocene-based material in which a description relating to the present invention can be seen. The invention relates to an invention of a propylene-based resin composition by two-stage polymerization using a catalyst. In paragraph 0013, an ethylene-based copolymer of a dispersion promoter (third component compatibilizer) using a metallocene catalyst is a multi-stage. Although it is described that it can be added by polymerization, this description is merely provided, and three-stage polymerization using a metallocene catalyst is not recommended. Not find anything, such as descriptions and examples. 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 0.01 500 g / 10 min ”is described (a summary of claim 1 on pages 97-98) and the impact resistance is improved by a compatibilizing agent (page 49-1 (3 lines) and two-component glass transition temperatures (1 page, 51 lines, 53 pages, 7 lines), but the contents of the literature are mostly descriptions of catalyst components and well-known matters. Since the description of the essence of the invention can hardly be found, as described in paragraph 0006 in the background art, the substance of the invention uses 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. Further, the propylene-based resin composition of the present invention is not disclosed at all from the point that the use of impact modifiers and elastomers is not described at all. Specifically, rigidity, heat resistance and impact resistance are not disclosed. It is difficult to clearly disclose a production method for a propylene-based resin composition having an excellent balance of properties.
On the other hand, the present invention has specific requirements for a specific configuration in the propylene-based block copolymer composition as an impact modifier used in the propylene-based resin composition as described above, As it improves heat resistance and impact resistance in a well-balanced manner, it also improves the appearance of molded products, such as flow marks, and has special effects such as special improvements in impact resistance at low temperatures. Therefore, it can be said that the description of the prior literature does not suggest or suggest the present invention.

  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 generally described. 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. The inventions [1] to [7] are collectively referred to as “the present invention”.

（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（ｂ−２）の配合比により、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。 [1] A propylene-based resin composition comprising the following components (I) to (IV):
Component (I): a propylene homopolymer component, or a crystalline propylene polymer component (a) composed of a copolymer of propylene with up to 3 wt% ethylene or an α-olefin having 4 to 20 carbon atoms, and 60 to 95 wt% Propylene-ethylene copolymer component (b) 40 to 5 wt%, each component is polymerized using a metallocene catalyst and satisfies the following characteristics i) to iv): 10-30% by weight of polymer composition
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 (b-2) having different ethylene contents, and the component (b-1) ethylene The content is 15 to 30 wt%, the ethylene content of the component (b-2) is 40 to 55 wt%, and the quantitative ratio (b-1) / (b-) of the component (b-1) and the component (b-2) 2) is in the range of 1:99 to 40:60.
Component (II): MFR (230 ° C., 21.18 N load) is 15 to 200 g / 10 minutes, and 30 to 80% by weight of a propylene block copolymer polymerized using a Ziegler catalyst
Component (III): 10 to 40% by weight of ethylene / α-olefin elastomer or styrene elastomer
Ingredient (IV): Inorganic filler: 0 to 50% by weight
[2] The propylene-based resin composition according to [1], wherein a propylene-based block copolymer composition (component (I)) that also satisfies the following property v) is used.
v) The peak temperature of tan δ derived from the propylene-ethylene copolymer component (b) obtained by solid viscoelasticity measurement at a frequency of 10 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 60. The propylene-based resin composition according to [1] or [2], wherein the propylene-based resin composition is [1] or [2].
[4] Any one of [1] to [3], wherein 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). Propylene-based resin composition.
[5] Each component in the propylene-based block copolymer composition (component (I)) is produced by sequential multi-stage polymerization, or individually polymerized components are mixed, or these steps are combined. The propylene-based resin composition according to any one of [1] to [4], which is manufactured by:
[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 impact resistance of the propylene-ethylene copolymer components (b-1) and (b-2) is increased in a synergistic manner depending on the blending ratio of the propylene-ethylene copolymer components (b-1) and (b-2). The propylene-type resin composition in any.

The present invention sufficiently improves the rigidity, heat resistance and impact resistance of the propylene-based resin material in a well-balanced manner, and also improves the appearance of the molded product, particularly the flow mark performance of the molded product, and further at low temperatures. The impact resistance can be improved.
In particular, by specifying the blending ratio of the two components of the propylene-ethylene copolymer, there is also a remarkable effect that the impact resistance is increased in synergy.

  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. Propylene-based block copolymer composition (component I)
(1) Basic rules for impact modifier made of propylene-based block copolymer composition i) Component and blending amount The basic rules for the propylene-based block copolymer (component I) of the present invention are propylene alone. 60 to 95 wt% of a crystalline propylene polymer component (a) composed of a polymer component, or a copolymer of propylene with up to 3 wt% ethylene or an α-olefin having 4 to 20 carbon atoms, and a propylene-ethylene copolymer Component (b) consists of 40 to 5 wt%, and each component is a propylene block copolymer that is polymerized using a metallocene catalyst. In addition, the mixing | blending of another component is not excluded.
The amount of the impact modifier that is a propylene-based block copolymer is 10 to 30% by weight of the entire propylene-based resin composition, preferably 12 to 25% by weight, more preferably 15 to 23% by weight. is there. If it is less than 10% by weight, the impact resistance improving effect is small, and if it exceeds 30% by weight, the appearance performance of the molded product is inferior.

ii) Melting point From the viewpoint of the rigidity and heat resistance of the composition, the propylene block copolymer composition preferably has a higher melting point, preferably 156 ° C or higher, preferably 157 ° C or higher, more preferably It is 158 degreeC or more.
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 copolymer composition, the melting point of the copolymer composition is the one observed at the highest temperature.
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 being excellent in rigidity and heat resistance. For that purpose, the crystalline propylene polymer component (a) (produced by the first-stage polymerization in the case of producing by multi-stage 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) Blending 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, the two or more stages are used). The sum of the weights of the components produced by the polymerization is defined as 40-5% 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)
I. 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 detailed measurement methods.
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-based 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 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 the copolymer and does not contain PP (propylene polymer), W ₄₀ contributes to the content of the copolymer derived from fraction 1 as it is in the whole. 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 characteristics of the propylene-based block copolymer composition of the present invention are propylene-ethylene random copolymer components ( b) 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 characteristic, that is, as emphasized in paragraph 0019, 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 phase having a high ethylene content and a propylene polymer component. It is a solubilizer 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 block copolymer composition of the present invention, the ethylene content of component (b-1) which is a compatibilizer component is 15 to 30 wt%. And 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. Moreover, the ethylene content of a component (b-2) is 40-55 wt%, It is characterized by the above-mentioned. 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 the blend components.

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 less than this range, the effect as a compatibilizing agent is reduced, and sufficient impact resistance cannot be obtained at both normal temperature and low temperature, and if this range is exceeded (b-2) 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 In the propylene block copolymer composition (component (I)) of the present invention, precise index control is required in the ethylene content, blending ratio and other regulations of the copolymer two components. In order to achieve this, it is necessary to produce the polymer with a metallocene catalyst that makes the molecular weight distribution and copolymer composition of the polymer 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, in the TREF of the above-described method, 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, 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-based block copolymer composition, as a whole of the propylene-based block copolymer composition, the glass transition temperature needs to be sufficiently low, In addition to defining the average ethylene content of the copolymer, it is necessary to define the glass transition temperature.
The propylene-based block copolymer composition of the present invention is obtained by solid viscoelasticity measurement that detects a stress generated by applying a sine strain to a strip-shaped sample piece in a range of −80 to 150 ° C. and a frequency of 10 Hz. The glass transition temperature (so-called tan δ peak temperature) of the copolymer component to be obtained 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 0 ° C., and the glass transition temperature derived from the copolymer component is higher than that. Although observed at a low temperature, 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. And 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 Block Copolymer Composition (Component (I)) (1) Metallocene Catalyst The polypropylene block copolymer composition of the present invention is preferably produced with a metallocene catalyst for all of its components. As described above, the metallocene copolymer having a higher melting point and excellent heat resistance and rigidity is disclosed below in order to be industrially easy to handle and inexpensive to manufacture, [A] A transition metal compound represented by the following general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B-2) a compound capable of reacting with a transition metal compound to form a cation, (B-3 ) It is preferable to use a catalyst having an activator comprising any one or more of ion-exchangeable layered compounds (including silicates) as an essential component and [C] an organoaluminum compound as an optional component. Properly, among which the [A] and (B-3) and is most preferably to use a catalyst consisting of an organoaluminum compound as an optional component.

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。 I. [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 that is 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 characteristic of the preferable 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. And having 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, 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 bonded to M. 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, the component [B] includes (B-1) an organoaluminum oxy compound, (B-2) a compound capable of reacting with a transition metal compound to form a cation, and (B-3) an ion-exchange layered compound. An activator comprising any one or more of (including silicates) is used.

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 . Can be obtained by 1: 1 (molar ratio) reaction.
The 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, chrysotile, lizardite, and serpentine such as 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 anokisite, halloysites such as metahalloysite and halloysite, serpentine groups such as chrysotile, lizardite and antigolite, montmorillonite, sauconite 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, 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.

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) Aspect of Production Method The block copolymer composition (component (I)) of the present invention comprises at least three components, and the production method is by melt-kneading, or multistage of three or more stages. A polymerization method can be employed. 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 When manufacturing by melt-kneading, for example, in the case of three components, the components (a), (b-1) and (b-2) themselves are separately polymerized and 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 for each component using a slurry method, a bulk method, a gas method. 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 produced by multi-stage polymerization of three or more stages are analyzed sequentially by the TREF-GPC-IR method after completion of each stage of the 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. Average molecular weight and ethylene content, Mw (b-1) and [E] (b-1) are the weight average molecular weight and ethylene content of component (b-1) determined 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 by using the 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. Propylene block copolymer (component (II))
(1) Basic rules The propylene-based block copolymer used as component (II) in the present invention is preferably a block copolymer obtained by two-stage polymerization of propylene and ethylene, and uses a Ziegler-based highly stereoregular catalyst. The slurry polymerization method, the gas phase polymerization method, or the liquid phase bulk polymerization method is preferably used, but it is preferably manufactured by the gas phase polymerization method from the viewpoint of paintability and cost. As the polymerization method, either batch polymerization or continuous polymerization can be adopted, but it is preferable to produce the polymerization by continuous polymerization.
In producing this propylene / ethylene block copolymer, a crystalline propylene homopolymer part is first formed by homopolymerization of propylene, and then an ethylene / propylene random copolymer part is formed by random copolymerization of propylene and ethylene. What was formed is preferable in terms of quality.

(2) Production method Specific production methods include a titanium trichloride catalyst composed of titanium trichloride and an organic aluminum halide, and a solid catalyst component containing magnesium chloride, titanium halide, and an electron donating compound as essential components. A method using a magnesium-supported catalyst composed of organoaluminum and an organosilicon compound, or a catalyst in which an organoaluminum compound component is combined with an organosilicon treatment solid catalyst component formed by contacting organoaluminum and an organosilicon compound as a solid catalyst component. And propylene homopolymerization, followed by random copolymerization of propylene and ethylene. Further, this propylene / ethylene block copolymer may be used within the range not significantly impairing the essence of the present invention, such as other unsaturated compounds, for example, α-olefins such as 1-butene, vinyl esters such as vinyl acetate, and maleic anhydride. It may be a ternary or higher copolymer containing an unsaturated organic acid or a derivative thereof, or a mixture thereof.

(3) Characteristic value The MFR of the propylene-based block copolymer is 15 to 200 g / 10 minutes, preferably 20 to 100 g / 10 minutes, and more preferably 25 to 70 g / 10 minutes. When the MFR is 15 g / 10 min or less, the MFR of the propylene-based resin composition is low, and the appearance performance of the molded product is deteriorated, which is not preferable. On the other hand, if it exceeds 200 g / 10 minutes, the impact resistance and elongation characteristics deteriorate, which is not preferable.
The crystalline polypropylene of the propylene block copolymer is 65 to 95% by weight, preferably 70 to 90% by weight, more preferably 75 to 85% by weight, and the propylene block copolymer is propylene / ethylene block copolymer. In the case of a coalescence, the ethylene / propylene copolymer part is 5 to 35% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight (provided that the crystalline polypropylene part and the ethylene / propylene copolymer part are The total amount of the polymer part is 100% by weight.).
The ethylene content of the ethylene / propylene copolymer part is 30 to 55% by weight, preferably 35 to 45% by weight.
The compounding quantity of a propylene-type block copolymer is 30 to 80 weight% in the whole composition, Preferably it is 35 to 70 weight%, More preferably, it is 40 to 60 weight%. If it is less than 30% by weight, the appearance performance of the molded product deteriorates, which is not preferable. If it exceeds 80% by weight, the balance of impact resistance deteriorates, which is not preferable.

4). Ethylene / α-olefin elastomer or styrene elastomer component (III)
(1) Basic rules The ethylene / α-olefin elastomer or styrene elastomer used as the component (III) in the present invention improves impact resistance and exhibits good moldability, physical properties and shrinkage characteristics. It is used for the purpose.
Examples of the comonomer copolymerized with ethylene in the ethylene / α-olefin elastomer include α-olefins having 4 to 20 carbon atoms, such as 1-octene and 1-butene. It may be a mixture of two or more ethylene / α-olefin elastomers or styrene elastomers. The content of 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. % By weight, preferably 10 to 40% by weight, with a density of 0.88 to 0.95 g / cm ³ , preferably 0.89 to 0.92 g / 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.

(2) Production Method The production of the ethylene / α-olefin elastomer can be obtained by polymerization using a known titanium 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.

(3) Blending amount The ethylene / α-olefin elastomer or styrene elastomer is 10 to 40% by weight in the whole composition, preferably 12 to 40% by weight, and particularly preferably 15 to 40% by weight in the case of using impact. 40% by weight. If the amount of the ethylene / α-olefin copolymer elastomer is less than 10% by weight, the effect of improving the impact is small, and if it exceeds 40% by weight, the rigidity and heat resistance of the propylene-based resin composition are greatly reduced, which is not preferable. .

5. Inorganic filler (component (IV)
Examples of the inorganic filler of component (IV) used in the present invention include talc, wollastonite, calcium carbonate, barium sulfate, mica, glass fiber, carbon fiber, clay, and organized clay, and preferably talc. , Mica, glass fiber and carbon fiber, particularly preferably talc. Talc is effective for improving rigidity and dimensional stability of molded products.
The particle size (including fiber diameter) of the inorganic filler varies depending on the inorganic compound used, but in the case of fibers, the fiber diameter is 3 to 40 μm, and in the case of granules, the particle diameter is about 1.5 to 150 μm.
In the case of talc, which is a suitable inorganic filler, the average particle size is preferably 1.5 to 40 μm, particularly preferably 2 to 15 μm. If the average particle size of talc is less than 1.5, the agglomeration causes the appearance to deteriorate, and if it exceeds 40 μm, the impact strength decreases, which is not preferable. In the case of granular talc, in general, for example, talc rough is first manufactured by pulverizing with an impact pulverizer or micron mill type pulverizer, or further pulverized with a jet mill or the like and then classified and adjusted with a cyclone or micron separator. Manufactured by. The talc may be surface-treated with various metal soaps, and so-called compressed talc having an apparent specific volume of 2.50 ml / g or less may be used.

The average particle size of the above-mentioned granular material is a value measured using a laser diffraction / scattering particle size distribution meter, and as a measuring device, for example, Horiba LA-920 type is preferable because of its excellent measurement accuracy. The fiber diameter of carbon fiber or glass fiber is generally calculated by cutting the fiber perpendicular to the fiber direction, observing the cross section under a microscope, measuring the diameter, and averaging 100 or more.
The compounding quantity in the whole composition of an inorganic filler is 0 to 50 weight%, Preferably it is 5 to 45 weight%, Most preferably, it is 10 to 40 weight%. When the amount of the inorganic filler exceeds 50% by weight, the impact resistance of the propylene-based resin composition is lowered, which is not preferable.

6). Production method of resin composition In the present invention, each component of the composition, that is, a propylene-based block polymer composition, a propylene-based block copolymer, an elastomer, an inorganic filler, and optional components used as necessary, etc. , By blending at the above blending ratio, kneading and granulating using a normal kneader such as a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, etc. A propylene-based resin composition is obtained.
In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is usually performed using a twin-screw extruder. In this kneading and granulation, the above-mentioned components may be kneaded simultaneously or sequentially. Further, each component is divided and kneaded in order to improve the performance, that is, for example, a part or all of the propylene-based block copolymer composition is first kneaded, and then the remaining components are kneaded and granulated. The method can also be adopted.

7). 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 brighteners, colorants, and conductivity-imparting agents can be added.
The amount of these additives is generally 0.0001 to 5% by weight, preferably 0.001 to 3% by weight, based on 100% by weight of the composition.

(2) Use of other resins In order to further 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. Other resins can also be blended.
As this additional component, polyethylene generally used as a compounding material for polyolefin resin, in particular, LDPE, HDPE , modified polypropylene, polycarbonate, polyamide, modified PPE, and the like can be added.
The compounding amount of these other resins is used within a range that does not impair the properties of the present resin composition, and is generally 0.5 to 10% by weight, preferably 1 to 5% by weight, based on 100% by weight of the composition.

(3) Applications Since the resin composition of the present invention is excellent in appearance performance of molded products and has sufficiently improved rigidity, heat resistance and impact resistance in a well-balanced manner, interior and exterior materials for vehicles such as automobiles and electrical products It is useful as various industrial materials such as packaging materials.
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 0029-0033.
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 calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Other details are described in paragraph 0034.
3) DSC
Measurements were made using a Seiko DSC. Other details are described in paragraph 0026.
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 0097 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. Load: 21.18N Die shape: 2.095 mm in diameter and 8.000 mm in length
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 using 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 Preparation method of 80mm test piece: Injection molding Condition adjustment: Leave in a constant temperature room adjusted to room temperature 23 ° C and humidity 50% for more than 24 hours Test room: Constant temperature room adjusted to room temperature 23 ° C and humidity 50% Number: 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 thermostatic 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: Cut notch in injection molded test piece (ISO 2818 compliant) State Adjustment: room temperature 23 ° C., humidity controlled at 50% in a constant temperature room for 24 hours or more Test room: room temperature 23 ° C., humidity controlled at 50% humidity Number of test pieces: 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) Suck 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.
10) Flow Mark Appearance Using a mold having a film gate with a width of 2 mm on the short side, an injection molding machine with a clamping pressure of 170 tons was injection-molded with a molding temperature of 220 ° C. and a molding sheet of 350 mm × 100 mm × 2 mmt. . The occurrence of the flow mark was visually observed, the distance from the gate to the portion where the flow mark was generated was measured, and judged according to the following criteria.
○: Generation distance exceeds 200 mm Δ: Generation distance exceeds 150 mm ×: Generation distance is 100 mm or less

[PP1] 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 mixtures);
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, 1.53 N) 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 prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) 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 with 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 stirrer) was mixed with a mixed gas of 72.5 vol% propylene, 27.5 vol% ethylene, 0.02 vol% hydrogen at 80 ° C. It was prepared with. Stirring of the polymerization tank is resumed, and after the inside of the polymerization tank is adjusted to a gas composition of 43 vol% propylene and 57 vol% ethylene, the previously prepared mixed gas is supplied so that the pressure in the polymerization tank becomes 1.5 MPa gauge pressure. Then, propylene / ethylene vapor phase copolymerization was carried out 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) was mixed with a mixed gas of propylene 44.99 vol%, ethylene 54.98 vol%, hydrogen 0.03 vol% at 80 ° C. It was prepared with. After the stirring of the polymerization tank is resumed and the inside of the polymerization tank is adjusted to a gas composition of 24 vol% propylene and 76 vol% ethylene, the previously prepared mixed gas is supplied so that the pressure in the polymerization tank becomes 2.0 MPa gauge pressure. Then, propylene / ethylene vapor phase copolymerization was carried out 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.

[PP2] Three-stage polymerization example The gas composition in the polymerization tank in the second step was 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step was 24 vol% in propylene and 76 vol% in ethylene, and other polymerizations A block copolymer was produced in the same manner as PP1 except that the 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.

[PP3] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1 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 PP3, the ethylene content in the second stage polymerization was too low and fractionation by TREF was insufficient, so the amount of copolymer component and the ethylene content were calculated from the results of the ethylene content and molecular weight of the sample extracted during the polymerization. Asked. As a result, the PP part Mw was 1.20 × 10 ⁵ , the copolymer part Mw was 38.8 × 10 ⁵ , the copolymer component content was 20 wt%, and the copolymer part ethylene content was 5 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.

[PP4] Production Examples of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. It was produced in the same manner as PP1 except that the gas composition in the polymerization tank in the second step was 54 vol% propylene and 46 vol% ethylene, and other polymerization conditions were as shown 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.

[PP5] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. It was produced in the same manner as PP1, 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.
[PP6] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1, except that the gas composition in the polymerization tank in the second step was 28 vol% propylene and 72 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[PP7] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. It was produced in the same manner as PP1, 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.
[PP8] Production example of intermediate component and base component for kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1, except that the gas composition in the polymerization tank in the second step was 28 vol% propylene and 72 vol% ethylene, and other polymerization conditions were as shown in Table 2.
[PP9] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1, 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.
[PP10] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1 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.
[PP11] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. It was produced in the same manner as PP1 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 described in Table 2.
[PP12] Production Example of Intermediate Component and Base Component for Kneading A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1, 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.
[PP13] Production Example of Intermediate Component for Kneading and Base Component A block copolymer was produced by two-stage polymerization. Production was carried out in the same manner as PP1, 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.

[PP14] Production example using Ziegler catalyst (preparation of solid catalyst component) 2,000 mL of dehydrated and deoxygenated n-heptane was introduced into a sufficiently nitrogen-substituted flask, and then 2.6 mol of MgCl ₂ and Ti (O the _{-n-C 4} H _{9) 4} were introduced 5.2 mol, the reaction was carried out for 2 hours at 95 ° C.. 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%.
(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)
First step polymerization: 3L autoclave with stirring and temperature controller was fully replaced with propylene, and then 4.82 mol of totriethylaluminum was diluted with n-heptane and added, followed by 5500 ml of hydrogen, followed by liquid propylene 750 g was 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 for 17 minutes at a polymerization temperature of 80 ° C. and a pressure of 2.0 MPaG. 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.

Component (II) Propylene-based block copolymer [Z-1] The amount of hydrogen in the first step is 4,500 ml, the gas composition in the polymerization tank in the second step is 62.3 vol% propylene, 34.3 vol% ethylene, hydrogen Other polymerization conditions were prepared in the same manner as PP14 except that 3.4 vol% and the polymerization time in the second step were 12 minutes.
The MFR of the propylene / ethylene block copolymer extracted from the second-stage polymerization tank of the samples obtained in these production examples is 30.5 g / 10 min. The coalescence component content was 18.3 wt% (according to formula (II)).
[Z-2] The amount of hydrogen in the first step is 750 ml, the gas composition in the polymerization vessel in the second step is 59.3 vol% propylene, 32.6 vol% ethylene, 8.1 vol% hydrogen, and the polymerization time in the second step is 12 Other polymerization conditions were the same as in PP14 except for the above.
The MFR of the propylene / ethylene block copolymer extracted from the second-stage polymerization tank of the samples obtained in these production examples was 3.1 g / 10 min. The coalescence component content was 17.3 wt% (according to formula (II)).
[Z-3] The amount of hydrogen in the first step is 7,000 ml, the gas composition in the polymerization vessel in the second step is 56.5 vol% propylene, 31.1 vol% ethylene, 12.4 vol hydrogen.
The other polymerization conditions were the same as PP14 except that 1% and the polymerization time of the second step was 10 minutes.
The MFR of the propylene / ethylene block copolymer extracted from the second-stage polymerization tank of the samples obtained in these production examples is 58.2 g / 10 min. The coalescence component content was 15.1 wt% (according to formula (II)).
[Z-4] The amount of hydrogen in the first step is 12,000 ml, the gas composition in the polymerization vessel in the second step is 57.2 vol% propylene, 40.0 vol% ethylene, 2.8 vol% hydrogen, and the polymerization time in the second step The other polymerization conditions were prepared in the same manner as PP14 except that was changed to 8 minutes.
The MFR of the propylene / ethylene block copolymer extracted from the second-stage polymerization tank of the samples obtained in these production examples is 105.5 g / 10 min. The coalescence component content was 11.1 wt% (according to formula (II)).

Component (III) Ethylene / α-olefin elastomer or styrene elastomer EOR-1: (Ethylene / octene rubber: ENGAGE 8100 manufactured by DuPont Dow) MFR = 2.0 g / 10 min SEBS-1: (Styrene / Ethylene / Butene) -Styrene block polymer rubber: Clayton G2657 manufactured by Shell Co., Ltd .: MFR = 9.0 g / 10 min EBM-1: (ethylene butene rubber: Tuffmer A1050S manufactured by Mitsui Chemicals): MFR = 2.4 g / 10 min

Ingredient (IV) Inorganic filler Fine powder talc (PKP53 manufactured by Fuji Talc): Average particle size 5.9 μm Aspect ratio 6

[Examples 1 to 16]
Each component (I)- (IV) was mix | blended in the ratio shown in Table 3, and the physical property evaluation was performed about what was granulated on the following conditions and shape | molded. The granulation conditions and molding conditions are shown below.
(Additive formulation) Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 0.05 wt% Tris (2,4-di- t-butylphenyl) phosphite 0.05% by weight, neutralizer: calcium stearate 0.1% by weight.
(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: 400 rpm Discharge amount: Adjusted to about 1.5 kg / hr with a screw feeder Die: 3 mm diameter Strand die Number of holes 2 (molded) The obtained raw material pellets were injection molded under the following conditions, A flat specimen for physical property evaluation was obtained. 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 time: 8 seconds Mold shape: flat plate (thickness 4 mm, width, 10 mm, length 80 mm) 2 index Resin composition index, TREF -Analyzed data and physical property data by GPC-IR are shown in Table 3 . The following examples are also shown in Table 3. The evaluation results are shown in Table 5.

[Comparative Examples 1-14]
Each component (I)- (IV) was mix | blended in the ratio shown in Table 4, and evaluation was performed similarly to the Example below. The evaluation results are shown in Table 6.

[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 which satisfies the respective 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 resin composition in which components (II) to (IV) are blended using the impact improving material which is the system block copolymer composition component (I), the flexural modulus and each of which is an index of rigidity It is clear that the balance between impact resistance at temperature is very good.
Furthermore, in each Example, the impact resistance at a low temperature (−30 ° C.) is improved, the flow mark of the appearance of the molded product is also good, and the characteristics of the present invention are the same. Since the copolymer component (b-1) having a low ethylene content as a solubilizer is blended under specific conditions, it can be seen that the impact resistance at each temperature also increases synergistically. Further, the heat resistance is balanced with other physical properties, and each example of the present invention is superior in balance of rigidity, impact resistance and heat resistance as compared with Comparative Example 9 using a Ziegler catalyst. .
In Comparative Examples 1 and 2, since the component (b-1) having a low ethylene content serving as a compatibilizer component is not included, the impact strength at each temperature is inferior and the flexural modulus is good. In addition, 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 component (b-1) is too low and the compatibility with component (b-2) deteriorates, resulting in poor impact resistance at each temperature. The ethylene content of the component (b-1) is too high, the compatibility with the component (a) is deteriorated, 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. Since the comparative example 10 has too little component (I) which is an impact improving material, its impact resistance is inferior. Since Comparative Example 11 has too little component (II), which is a propylene-based block copolymer by a Ziegler-based catalyst, the appearance performance is inferior. In Comparative Example 12, since the elastomer is not blended, the impact resistance is very poor. In Comparative Example 13, since the component (II), which is a propylene block copolymer based on a Ziegler catalyst, is too small and the amount of talc is too large, the impact resistance is remarkably lowered and the appearance performance is also poor. In Comparative Example 14, since the MFR of the component (II) that is a propylene-based block copolymer by a Ziegler-based catalyst is low, the MFR of the propylene-based resin composition is decreased, and thus the appearance performance is also decreased.
From the results and discussions of the examples and comparative examples described above, the rationality and significance of each requirement of the constitution of the present invention were proved, and in particular, the impact modifier in the component (I) of the present invention. As well as the exceptionalness of the present invention over the prior art.

Claims (5)

A propylene-based resin composition comprising the following components (I) to (IV):
Component (I): a propylene homopolymer component, or a crystalline propylene polymer component (a) composed of a copolymer of propylene with up to 3 wt% ethylene or an α-olefin having 4 to 20 carbon atoms, and 60 to 95 wt% Propylene-ethylene copolymer component (b) 40 to 5 wt%, each component is polymerized using a metallocene catalyst and satisfies the following characteristics i) to iv): 10-30% by weight of polymer composition
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 (b-2) having different ethylene contents, and the component (b-1) ethylene The content is 15 to 30 wt%, the ethylene content of the component (b-2) is 40 to 55 wt%, and the quantitative ratio (b-1) / (b-) of the component (b-1) and the component (b-2) 2), 1: 99 to 40: 60 range near the is, propylene - weight average molecular weight of the component of the ethylene copolymer (b-1) and component (b-2) are both 250,000～1,000 And the weight average molecular weight of component (a) is 60,000 to 250,000 .
Component (II): a propylene / ethylene block copolymer having an MFR (230 ° C., 21.18 N load) of 15 to 200 g / 10 minutes and polymerized using a Ziegler catalyst, 30-80% by weight of propylene / ethylene block copolymer having a coalescence part of 5-35% by weight
Component (III): 10 to 40% by weight of ethylene / α-olefin elastomer or styrene elastomer
Ingredient (IV): Inorganic filler: 0 to 50% by weight The propylene-based resin composition according to claim 1, wherein a propylene-based block copolymer composition (component (I)) that also satisfies the following property v) is used.
v) The peak temperature of tan δ derived from the propylene-ethylene copolymer component (b) obtained by solid viscoelasticity measurement at a frequency of 10 Hz in the range of -80 to 150 ° C is -47 ° C or lower. The propylene-based copolymer according to claim 1 or 2 , wherein 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). Resin composition. Each component in the propylene-based block copolymer composition (component (I)) is produced by sequential multi-stage polymerization, or individually polymerized components are mixed, or produced by combining these steps. The propylene-based resin composition according to any one of claims 1 to 3 , wherein 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. A compound capable of forming a cation, (B-3) an activator comprising at least one of the ion-exchangeable layered compounds (including silicates) 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 4 , which 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.)