Propylene-based block copolymers and propylene-based resin compositions

Abstract

To provide a propylene-based material which, when mixed with a rubber component and the like and used for a molded body, has excellent flowability in a mold and can produce a molded body having excellent impact resistance.SOLUTION: A propylene-based block copolymer satisfies the following (1) to (4). (1) A content of Dsol is 10-50 mass%, intrinsic viscosity [η] of the Dsol is 2.0-6.0 dl / g, and an ethylene content of the Dsol is 30-80 mol%, (2) MFR of the copolymer is 1-500 g / 10 minutes, (3) a melting point of the copolymer is 155-170°C, and (4) when angular frequencies at which storage elastic moduli become 102 Pa and 104 Pa in viscoelasticity measurement are represented by ω1 and ω2, respectively, and a product of the amount (mass%) of the Dsol and the intrinsic viscosity (dl / g) of the Dsol is represented by α, then in a double logarithmic plot of -α of the following formula (A), the following formula (B) and formula (C) are satisfied. Formula (A): ω2 / 10ω1, formula (B): 5.88×ln(α)-21.1<ln(formula (A))<5.88×ln(α)-17.8, and formula (C): 2≤ln(formula (A))≤6.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to propylene-based block copolymers and propylene-based resin compositions. [Background technology]

[0002] Propylene polymers have a wide range of applications as materials with excellent rigidity and heat resistance. Among propylene polymers, propylene block copolymers, which are produced by introducing amorphous copolymer components of propylene and other olefins (such as ethylene) through multi-stage polymerization, also exhibit excellent impact resistance in addition to the properties mentioned above. For this reason, propylene block copolymers are widely used as materials for automotive parts such as bumpers, instrument panels (dashboards), door trims, and pillars.

[0003] For example, Patent Document 1 describes a propylene-based block copolymer that satisfies predetermined requirements, obtained by producing a propylene-based polymer component (1) in the first step, a propylene-based copolymer component (2) in the presence of component (1) in the second step, and an ethylene-based copolymer component (3) in the presence of component (1) and component (2) in the third step. The patent document aims to provide a propylene-based block copolymer that has an excellent balance of rigidity, impact resistance, and low-temperature impact resistance when molded, and satisfies predetermined requirements. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2008 / 072790 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, when the conventional propylene-based block copolymer is mixed with a rubber component or the like and used for a molded body, there is still room for further improvement from the viewpoints of fluidity in a mold and impact resistance of the molded body.

[0006] An object of the present invention is to provide a propylene-based material capable of producing a molded body having excellent fluidity in a mold and excellent impact resistance when mixed with a rubber component or the like and used for the molded body.

Means for Solving the Problems

[0007] As a result of investigations to solve the above problems, the present inventors have found that the above problems can be solved by the propylene-based block copolymer described below, and have completed the present invention. The present invention relates to, for example, the following [1] to

[11] .

[0008] [1] A propylene-based block copolymer satisfying the following requirements (1) to (4). Requirement (1): The amount of the n-decane soluble part at 23°C is 10 to 50% by mass, the intrinsic viscosity [η] of the n-decane soluble part at 23°C measured in tetralin at 135°C is 2.0 to 6.0 dl / g, and the ethylene content of the n-decane soluble part at 23°C is 30 to 80 mol%. Requirement (2): The melt flow rate (at 230°C, 2.16 kg load) is 1 to 500 g / 10 min. Requirement (3): The melting point measured by a differential scanning calorimeter is 155 to 170°C. Requirement (4): In viscoelasticity measurement, the storage elastic modulus is 10 , ,

[0008] , , , 2 , 4 , , , , , , , Pa, 10 4 Let the angular frequencies (rad / s) at which the storage elastic modulus becomes 10 Pa and 10 Pa be ω1 and ω2, respectively, and let the product of the amount of the n-decane soluble part at 23°C (mass%) and the intrinsic viscosity of the n-decane soluble part at 23°C (dl / g) be α. Then, in the double logarithmic plot of the following formula (A)-α, both the following formula (B) and formula (C) are satisfied. ω2 / 10ω1 …(A) [[ID=३९]]5.88×ln(α)-21.1<ln(Formula (A))<5.88×ln(α)-17.8 …(B) 2≦ln(Formula (A))≦6 …(C)

[0009] [2] Furthermore, the propylene-based block copolymer of [1] that satisfies the following requirements (5) to (6). Requirement (5): 23°C n-decane insoluble portion 13 The mesopentade fraction (mmmm fraction) measured by 13C-NMR is 96.0–99.9%. Requirement (6): The melt flow rate of the n-decane-insoluble portion at 23°C (230°C, 2.16 kg load) is 50-1000 g / 10 min.

[0010] [3] A propylene resin composition containing the propylene block copolymer described in [1] or [2] above.

[0011] [4] The propylene resin composition [3] further contains an inorganic filler (F).

[0012] [5] 50 to 99 parts by mass of the propylene-based block copolymer described in [1] or [2], and The inorganic filler (F) is 1 to 50 parts by mass (provided that the total amount of propylene-based block copolymer and inorganic filler (F) is 100 parts by mass). A propylene resin composition containing the aforementioned [4].

[0013] [6] The propylene resin composition [3] further contains an elastomer (E).

[0014] [7] 50 to 99 parts by mass of the propylene-based block copolymer described in [1] or [2], and The elastomer (E) is 1 to 50 parts by mass (provided that the total amount of propylene-based block copolymer and elastomer (E) is 100 parts by mass). A propylene resin composition containing the aforementioned [6].

[0015] [8] 50 to 98 parts by mass of the propylene-based block copolymer described in [1] or [2] above, Inorganic filler (F) in 1 to 49 parts by mass, and Elastomer (E) 1 to 49 parts by mass (provided that the total amount of propylene-based block copolymer, inorganic filler (F), and elastomer (E) is 100 parts by mass). A propylene-based resin composition containing this resin.

[0016] [9] A molded article formed from the propylene-based block copolymer of [1] or [2] or any of the propylene-based resin compositions of [3] to [8].

[0017]

[10] The molded body of the aforementioned [9] is an injection-molded body.

[0018]

[11] A molded body of the aforementioned [9] or

[10] which is an automobile part. [Effects of the Invention]

[0019] The propylene-based block copolymer of the present invention, when mixed with rubber components or the like and used in molded articles, can produce molded articles that exhibit excellent fluidity within the mold and have excellent impact resistance. [Brief explanation of the drawing]

[0020] [Figure 1] Figure 1 shows the relationship between the storage modulus and angular frequency in requirement (4). [Figure 2] Figure 2 shows the relationship between ln(Equation (A)) and ln(α) in requirement (4). [Modes for carrying out the invention]

[0021] The present invention will be described in more detail below. [Propylene-based block copolymer] The propylene block copolymer according to the present invention is characterized by satisfying the following requirements (1) to (4).

[0022] (Requirement (1)) Requirement (1) is that the amount of the 23°C n-decane soluble part (hereinafter also referred to as "D" sol ) of the propylene block copolymer is 10 to 50% by mass, and the intrinsic viscosity [η] of D sol measured in tetralin at 135°C is 2.0 to 6.0 dl / g, and the ethylene content of D sol is 30 to 80 mol%.

[0023] In the propylene block copolymer of the present invention, the 23°C n-decane soluble part (D sol ) is usually a component mainly composed of constitutional units derived from propylene and ethylene. D sol is a component that does not show crystallinity or has low crystallinity, has a low glass transition temperature, exhibits impact resistance, and is considered to exhibit compatibility with other polymers when mixed with other polymers. This is sometimes referred to as a rubber component.

[0024] On the other hand, in the propylene block copolymer of the present invention, the 23°C n-decane insoluble part (hereinafter also referred to as "D" insol ) is usually a component mainly composed of constitutional units derived from propylene, and is considered to have crystallinity and exhibit high rigidity.

[0025] D sol The ratio of is preferably 10 to 40% by mass, more preferably 15 to 35% by mass. Note that the sum of the ratio of D sol and the ratio of D insol is 100% by mass. D sol When the ratio of is below the above range, the impact resistance of the molded body obtained from the propylene block copolymer tends to decrease. It is considered that this is because the energy absorbed against impact decreases as the ratio of D sol decreases.

[0026] Meanwhile, D sol If the proportion exceeds the above range, the high-speed moldability using propylene-based block copolymer may be poor, and the rigidity (buckling strength) of the molded article obtained from the propylene-based block copolymer may be poor.

[0027] The aforementioned D sol The ratio and the D insol The proportions are those measured using the method employed in the examples described later. D sol The intrinsic viscosity of the compound in decalin at 135°C is preferably 3.0 to 6.0 dl / g, more preferably 3.0 to 5.0 dl / g.

[0028] If the intrinsic viscosity exceeds or falls below the above range, the impact resistance of the molded article obtained from the propylene-based block copolymer may decrease. The intrinsic viscosity values ​​mentioned above were measured using the method employed in the examples described later.

[0029] D sol The proportion of ethylene-derived constituent units in the mixture is preferably 35 to 60 mol%, more preferably 40 to 55 mol%. If the proportion of the aforementioned constituent units falls below the above range, the impact resistance of the molded article obtained from the propylene-based block copolymer tends to be poor. sol This is thought to be because a decrease in the proportion of ethylene lowers the glass transition temperature, increases the degree of crystallinity, and reduces the energy absorbed by impact.

[0030] On the other hand, if the proportion of the aforementioned constituent units exceeds the above range, the high-speed moldability of the material containing the propylene-based block copolymer may be poor. The proportions of the aforementioned constituent units are those measured using the method adopted in the embodiments described later.

[0031] (Requirement (2)) Requirement (2) is that the melt flow rate (hereinafter also referred to as "MFR") of the propylene-based block copolymer (according to ASTM D-1238, 230°C, 2.16 kg load) is 1 to 500 g / 10 min. The MFR is preferably 10 to 300 g / 10 min, and more preferably 30 to 150 g / 10 min. If the MFR falls below the above range, short shots may occur when injection molding materials containing propylene-based block copolymers. Conversely, if the MFR exceeds the above range, burrs may occur when injection molding materials containing propylene-based block copolymers.

[0032] (Requirement (3)) Requirement (3) states that the melting point measured by a differential scanning calorimetry (DSC) is between 155 and 170°C. The details of the measurement conditions are as follows. Specifically, in accordance with JIS K7121, measurements are performed using a differential scanning calorimetry (DSC) under the following conditions, and the temperature at the peak of the endothermic peak in step 3 is defined as the melting point. If there are multiple endothermic peaks, the temperature at the peak of the largest endothermic peak is defined as the melting point.

[0033] (Measurement conditions) Atmosphere: Nitrogen gas atmosphere Sample amount: 5 mg Sample shape: Pressed film (molded at 230°C, thickness 200-400 μm) Step 1: Increase the temperature from 30°C to 240°C at a rate of 10°C / min, and hold for 10 minutes. Step 2: Cool the temperature down to 60°C at a rate of 10°C / minute. Step 3: Increase the temperature to 240°C at a rate of 10°C / min.

[0034] The melting point is preferably 160 to 170°C. If the melting point falls below the above range, the heat resistance of molded articles formed using propylene-based block copolymers may be poor.

[0035] (Requirement (4)) Requirement (4) is that in the viscoelasticity measurement of the propylene-based block copolymer, when the storage modulus is 10 2 Pa and 10 4 Pa, the angular frequencies (rad / s) are ω1 and ω2 respectively. Let the product of the amount (mass %) of the D sol and the intrinsic viscosity [η] (dl / g) of the D sol be α. Then, in the double logarithmic plot of the following formula (A)-α, both the following formula (B) and formula (C) are satisfied ω2 / 10ω1 …(A) 5.88×ln(α)-21.1 < ln(formula (A)) < 5.88×ln(α)-17.9 …(B) 2 ≦ ln(formula (A)) ≦ 6 …(C) The technical significance of requirement (4) will be described while referring to FIGS. 1 and 2.

[0036] FIG. 1 shows the relationship between the storage modulus and the angular frequency in the viscoelasticity measurement of a propylene-based block copolymer having a propylene homopolymer part (hereinafter also referred to as "homo-PP part") and a propylene-ethylene copolymer part (hereinafter also referred to as "rubber part").

[0037] Formula (A) relates to the ratio of the angular frequencies at two storage moduli of the propylene-based block copolymer as shown in FIG. 1. The higher the ratio of the rubber part to the homo-PP part, the slower the relaxation rate at a low shear rate, and the smaller ω1 becomes, so the value of formula (A) becomes larger. ···(i) The larger the intrinsic viscosity [η] of the rubber part, the slower the relaxation rate at a low shear rate, and the smaller ω1 becomes, so the value of formula (A) becomes larger. ···(ii) In addition, in the sea-island structure formed in the propylene-based block copolymer, the better the dispersibility of the rubber, the larger the surface area of the rubber part as the island phase, so the friction with the homo-PP part as the sea phase becomes larger, and as a result, the value of formula (A) becomes larger. ···(iii) From the above, it can be said that the value of formula (A) determined by the ratio of the rubber part and the intrinsic viscosity [η] of the rubber part becomes larger when the dispersibility of the rubber part is excellent.

[0038] The flow curve is a logarithmic plot of the storage modulus and angular frequency. Considering (i) and (ii) above, when the logarithm of the product of the proportion of rubber and the intrinsic viscosity [η] of the rubber is fixed, a large logarithm of the value of equation (A) is due to (iii) above, meaning that the dispersibility of the rubber is excellent in the sea-island structure.

[0039] Figure 2 shows the relationship between ln(Equation (A)) and ln(α) in requirement (4), with the area enclosed by the central rectangle representing the range that satisfies requirement (4). The coefficient of ln(α) was determined based on the examples described later. D sol The amount and D sol The intrinsic viscosity [η] of each corresponds to the proportion of the rubber portion (hereinafter also referred to as "rubber amount") and the intrinsic viscosity [η] of the rubber portion (hereinafter also referred to as "rubber [η]"), and D sol The amount and D sol The product α of the rubber and its intrinsic viscosity [η] corresponds to the product of the proportion of the rubber and the intrinsic viscosity [η] of the rubber (hereinafter also referred to as "amount of rubber × rubber [η]").

[0040] The relationship between the amount of rubber and rubber[η] can be broadly divided into: 1. The amount of rubber is small, and the rubber [η] is large. 2. The amount of rubber is small, and the rubber [η] is small. 3. A large amount of rubber and a large rubber [η]. 4. The amount of rubber is large, and the rubber [η] is small. There are four patterns.

[0041] Since the range of rubber quantity is 0 to 100% by mass, while the range of rubber[η] is approximately 0 to 10 dl / g, the product of rubber quantity and rubber[η] (hereinafter also referred to as "rubber quantity × rubber[η]") is more significantly affected by changes in rubber quantity than by changes in rubber[η].

[0042] D corresponding to the amount of rubber sol The amount, and D corresponding to rubber [η] solIf the intrinsic viscosity [η] does not satisfy requirement (1), the relationship between ln(α) and ln(equation (A)) is thought to change as follows.

[0043] 1. When the amount of rubber is small and the rubber [η] is large: Although ln(α) is small due to the small amount of rubber, it is thought that ln(Equation (A)) will be large because the amount of rubber[η] is large (region (1) in Figure 2).

[0044] 2. When the amount of rubber is small and the rubber [η] is too small: As ln(α) decreases, ln(Equation (A)) is also expected to decrease. (Region (2) in Figure 2).

[0045] 3. When there is too much rubber and the rubber [η] is too large: It is thought that as ln(α) increases, ln(Equation (A)) also increases. (Region (3) in Figure 2).

[0046] 4. When the amount of rubber is large and the rubber [η] is small: Although ln(α) is large due to the large amount of rubber, it is thought that ln(Equation (A)) will be small because the amount of rubber[η] is small (region (4) in Figure 2).

[0047] When considering the use of propylene-based block copolymers as automotive materials, the following problems are expected to occur in the propylene-based block copolymers in regions (1) to (4) in Figure 2.

[0048] Area(1): Due to the low amount of rubber, there is a risk of reduced impact resistance. Furthermore, because the amount of rubber is low and the rubber[η] is high, the dispersion of components with high rubber[η] is poor, which may lead to the formation of blemishes and worsen surface impact resistance. Area(2): Because ln(α) is small, and both the amount of rubber and rubber[η] are small, there is a risk of low impact resistance. . Area(3): Since both the rubber content and the rubber [η] are large, the fluidity decreases, and there is a risk that the moldability will be poor. Region (4): The polymer mixture of Comparative Example A1 described later and the copolymer used for its preparation belong to Region (4). The propylene-based block copolymer in Region (4) may have a poor balance between rigidity and impact resistance, similar to the comparative examples.

[0049] Regarding the comparative examples in detail, the polymers (propylene-based copolymers with a single-stage copolymerization tank) produced in Polymer Production Examples 1 and 2 described later do not contain high molecular weight components. Therefore, since the value of ln(formula (A)) is lower than that of the propylene-based block copolymer of the present invention, they belong to Region (4).

[0050] Although the polymer mixture of Comparative Example A1 (an extruder melt blend product of the polymers produced in Polymer Production Examples 1 and 2) contains high molecular weight components, its dispersibility is inferior to that of the propylene-based block copolymer of the present invention. As a result, the surface area of the rubber part, which is the island phase of the sea-island structure, becomes small, and the friction with the homopolymer PP part, which is the sea phase, becomes small. Therefore, it is considered that the value of ln(formula (A)) becomes smaller than that of the propylene-based block copolymer of the present invention, and a polymer mixture like Comparative Example A1 exists in Region (4) (or Region (2)).

[0051] On the other hand, the propylene-based block copolymer in the central rectangular region of FIG. 2, that is, the propylene-based block copolymer of the present invention that satisfies requirement (4), has no or suppressed the above-mentioned problems that occur in Regions (1) to (4). Therefore, it is particularly suitable for use as an automotive material.

[0052] The propylene-based block copolymer of the present invention preferably satisfies the following formula (B'), and more preferably satisfies the following formula (B"). 5.88×ln(α)-20.8 < ln(formula (A)) < 5.88×ln(α)-17.8 …(B') 5.88×ln(α)-20.5 < ln(formula (A)) < 5.88×ln(α)-18.1 …(B")

[0053] The propylene-based block copolymer of the present invention preferably satisfies the following formula (C'), and more preferably the following formula (C"). 3≦ln(Formula (A))≦6 …(C') 4≦ln(Formula (A))≦5.5 …(C")

[0054] A propylene-based block copolymer that satisfies requirement (4) can be produced, for example, by continuously polymerizing the rubber portion in two stages: a step to produce a rubber portion with a high ethylene content and low intrinsic viscosity [η], and a step to produce a rubber portion with a low ethylene content and high intrinsic viscosity [η], as described later. The propylene-based block copolymer of the present invention preferably satisfies the following requirement (5).

[0055] (Requirement (5)) Requirement (5) is the aforementioned D insol of 13 The mesopentade fraction (mmmm fraction) measured by 13C-NMR is 96.0 to 99.9%. Details of the measurement conditions are described in the Examples section below. The mesopentade fraction (mmmm fraction) is preferably 97.0 to 99.9%. When requirement (5) is met, the stereoregularity of the homo-PP portion is high, resulting in a high degree of crystallinity during crystallization, and thus the propylene-based block copolymer becomes highly rigid. The propylene-based block copolymer of the present invention preferably satisfies the following requirement (6).

[0056] (Requirement (6)) Requirement (6) is as described in D insol The melt flow rate (MFR) (230°C, load 2.16 kg) is 50 to 1000 g / 10 min. Preferably, the MFR is 80 to 800 g / 10 min, and more preferably 100 to 500 g / 10 min. When requirement (6) is met, the propylene-based block copolymer of the present invention exhibits excellent fluidity when injection molding. Furthermore, the propylene-based block copolymer of the present invention may also contain constituent units derived from biomass-derived propylene and / or biomass-derived ethylene. The monomers constituting the polymer (propylene and / or ethylene) may consist solely of biomass-derived monomers (propylene and / or ethylene), solely of fossil fuel-derived monomers (propylene and / or ethylene), or may contain both biomass-derived monomers (propylene and / or ethylene) and fossil fuel-derived monomers (propylene and / or ethylene). Biomass-derived propylene and biomass-derived ethylene are monomers derived from any renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, and are derived from plants or animals, and contain 1 × 10⁻¹⁶ 14C isotopes as carbon. -12 It contains a certain proportion, and the biomass carbon concentration (pMC) measured according to ASTM D6866 is approximately 100 pMC. Biomass-derived propylene and biomass-derived ethylene can be obtained, for example, by conventionally known methods. It is preferable from the viewpoint of reducing environmental impact that the propylene-based block copolymer of the present invention contains constituent units derived from biomass-derived propylene and / or biomass-derived ethylene. If the polymer production conditions such as polymerization catalyst and polymerization temperature are the same, even if the raw material propylene is a propylene-based block copolymer containing biomass-derived propylene and / or biomass-derived ethylene, the 14C isotope is 1 × 10⁻¹⁶. -12 Aside from the proportions it contains, its molecular structure is equivalent to that of propylene-ethylene block polymers, which consist of fossil fuel-derived propylene and fossil fuel-derived ethylene. Therefore, its performance is considered to be the same as these.

[0057] [Method for producing propylene-based block copolymers] The propylene-based block copolymer of the present invention is, for example, Step (1) for producing a propylene-based polymer component (1), A step (2A) of producing a propylene copolymer component (2A) in the presence of the propylene polymer component (1), and A step (2B) to produce a propylene copolymer component (2B) in the presence of the propylene copolymer component (1) and the propylene copolymer component (2A). It can be manufactured by a manufacturing method that includes these in this order and satisfies the requirements (i) to (iv) described below.

[0058] (Requirement (i)) Requirement (i) is that either the propylene copolymer component (2A) or the propylene copolymer component (2B) has an ethylene-derived constituent unit content (hereinafter also referred to as "ethylene content"; the total amount of constituent units in each copolymer component is set to 100 mol%) of 40 to 80 mol%, and an intrinsic viscosity [η] measured in tetralin at 135°C of 1.5 to 4.0 dl / g. The ethylene content is preferably 45-70 mol%, and more preferably 50-60 mol%. Furthermore, the intrinsic viscosity [η] is preferably 2.0 to 4.0 dl / g, and more preferably 2.0 to 3.5 dl / g. Requirement (i) is satisfied by, of the two propylene copolymer components, preferably the propylene copolymer component (2A).

[0059] (Requirement (ii)) Requirement (ii) is that the other of the propylene copolymer component (2A) or the propylene copolymer component (2B) has an ethylene content of 30-50 mol% and an intrinsic viscosity [η] of 5.0-10 dl / g as measured in tetralin at 135°C. The ethylene content is preferably 35-50 mol%, and more preferably 35-48 mol%. Furthermore, the intrinsic viscosity [η] is preferably 6.0 to 10 dl / g, and more preferably 7.0 to 10 dl / g. Requirement (ii) is preferably satisfied by the propylene copolymer component (2B) among the two propylene copolymer components.

[0060] (Requirement (iii)) Requirement (iii) is that the mass ratio of propylene copolymer component (2A) to propylene copolymer component (2B) (i.e., mass of component (2A) / mass of component (2B); hereinafter also referred to as "mass ratio (iii)") is between 10 / 1 and 1 / 1. The mass ratio (iii) is 8 / 1 to 2 / 1, more preferably 6 / 1 to 2 / 1. If the mass ratio (iii) exceeds the above upper limit, the balance between rigidity and impact resistance may be poor, and if it falls below the above lower limit, the fluidity may decrease, potentially leading to molding defects.

[0061] (Requirement (iv)) Requirement (iv) is that the mass ratio of propylene polymer component (1) to propylene copolymer component (2A) and propylene copolymer component (2B) (i.e., the mass of component (1) / the total mass of components (2A) and (2B). Hereinafter also referred to as "mass ratio (iv)") is between 10 / 1 and 1 / 1. The mass ratio (iv) is preferably 8 / 1 to 1 / 1, and more preferably 6 / 1 to 2 / 1. If the mass ratio (iv) exceeds the upper limit above, impact resistance may decrease, and if it falls below the lower limit above, fluidity may decrease, potentially leading to molding defects.

[0062] <Processes (1), (2A), and (2B)> In steps (1), (2A), and (2B) described above, homopolymerization of propylene or copolymerization of propylene and ethylene is usually carried out in the presence of a metallocene compound-containing catalyst or a Ziegler-Natta catalyst, preferably in the presence of a Ziegler-Natta catalyst. Polymerization in the presence of a Ziegler-Natta catalyst easily yields propylene-based block copolymers with a broad molecular weight distribution and good moldability.

[0063] (Catalyst containing metallocene compound) Examples of metallocene compound-containing catalysts include metallocene catalysts comprising a metallocene compound, at least one compound selected from organometallic compounds, organoaluminum oxy compounds, and compounds capable of forming ion pairs in reaction with metallocene compounds, and optionally a particulate support. Preferably, metallocene catalysts capable of stereoregular polymerization such as isotactic are used. Among the metallocene compounds, crosslinkable metallocene compounds exemplified in International Publication No. 01 / 27124 and metallocene compounds described in sections

[0068] to

[0076] of International Publication No. 2010 / 74001 are preferred. Furthermore, compounds that form ion pairs in reaction with organometallic compounds, organoaluminum oxy compounds, and transition metal compounds, and optionally a particulate support, can be used without limitation from compounds disclosed in International Publication No. 01 / 27124, Japanese Patent Application Publication No. 11-315109, etc.

[0064] (Ziegranata catalyst) Propylene-based block copolymers can be produced using a highly stereoregular Ziegler-Natta catalyst. Various known catalysts can be used as the highly stereoregular Ziegler-Natta catalyst. For example, a catalyst can be used comprising (a) a solid titanium catalyst component containing magnesium, titanium, a halogen, and an electron donor, (b) an organometallic compound catalyst component, and (c) an organosilicon compound catalyst component having at least one group selected from the group consisting of cyclopentyl, cyclopentenyl, cyclopentadienyl, and derivatives thereof. This catalyst component can be produced by known methods, for example, by the methods described in International Publication No. 2010 / 74001, sections

[0078] to

[0094] .

[0065] When polymerizing propylene using a catalyst consisting of the solid titanium catalyst component (a), organometallic compound catalyst component (b), and organosilicon compound catalyst component (c) as described above, prepolymerization can also be performed beforehand. Prepolymerization involves polymerizing an olefin in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and optionally the organosilicon compound catalyst component (c).

[0066] As the olefin for prepolymerization, α-olefins having 2 to 8 carbon atoms can be used. Specifically, linear olefins such as ethylene, propylene, 1-butene, and 1-octene; branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene can be used. These may also be copolymerized.

[0067] Prepolymerization should be carried out so that approximately 0.1 to 1000 g, preferably 0.3 to 500 g, of polymer is produced per 1 g of solid titanium catalyst component (a). If the amount of prepolymerization is too large, the efficiency of (co)polymer formation in the main polymerization may decrease. In prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system during the main polymerization.

[0068] For this polymerization, it is desirable to use solid titanium catalyst component (a) (or prepolymerization catalyst) in an amount of approximately 0.0001 to 50 millimoles, preferably approximately 0.001 to 10 millimoles, of titanium atoms per liter of polymerization volume. For organometallic compound catalyst component (b), it is desirable to use an amount of approximately 1 to 2000 moles, preferably approximately 2 to 500 moles, of metal atoms per mole of titanium atoms in the polymerization system. For organosilicon compound catalyst component (c), it is desirable to use an amount of approximately 0.001 to 50 moles, preferably approximately 0.01 to 20 moles, of organometallic compound catalyst component (b) per mole of metal atoms.

[0069] Polymerization may be carried out by gas-phase polymerization, solution polymerization, suspension polymerization, or any other liquid-phase polymerization method, and steps (1), (2A), and (2B) may be carried out separately. Furthermore, it may be carried out in a continuous or semi-continuous manner, and each of the above steps may be divided and carried out in multiple polymerizers, for example, 2 to 10 polymerizers. Industrially, polymerization is most preferably carried out in a continuous manner.

[0070] Inert hydrocarbons may be used as the polymerization medium, or liquid propylene may be used as the polymerization medium. The polymerization conditions for each stage are appropriately selected within the range of atmospheric pressure to 10 MPa (gauge pressure), preferably 0.2 to 5 MPa (gauge pressure), with a polymerization temperature of approximately -50 to +200°C, preferably approximately 20 to 100°C, and a polymerization pressure of atmospheric pressure to 10 MPa (gauge pressure).

[0071] In the manufacturing method of the present invention, for example, steps (1), (2A), and (2B) are carried out continuously in a reaction apparatus in which three or more polymerizers are connected in series. Alternatively, step (1) may be carried out in each polymerization apparatus using a polymerization apparatus in which two or more reactors are connected in series, or step (2A) may be carried out in each polymerization apparatus using a polymerization apparatus in which two or more reactors are connected in series, or step (2B) may be carried out in each polymerization apparatus using a polymerization apparatus in which two or more reactors are connected in series.

[0072] Step (1) is a step in which propylene and optionally ethylene are polymerized at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa gauge pressure, wherein ethylene is not supplied, or a small amount of ethylene is supplied compared to the amount of propylene fed, D insol This is a process for producing the propylene-based polymer component (1), which is the main component of the product. Additionally, if necessary, a chain transfer agent such as hydrogen gas may be introduced to adjust the intrinsic viscosity [η] of the propylene-based polymer component (1) produced in process (1).

[0073] Step (2A) is a step in which propylene and ethylene are copolymerized in the presence of a propylene-based polymer component (1) at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa gauge pressure, and by making the ratio of the amount of ethylene feed to the amount of propylene feed larger than in step (1), D sol This is a process for producing the propylene copolymer component (2A) of the propylene-ethylene copolymer rubber, which is the main component of the product. In addition, a chain transfer agent, such as hydrogen gas, may be introduced as needed to adjust the intrinsic viscosity [η] of the propylene copolymer component (2A).

[0074] Step (2B) is a step in which propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa gauge pressure in the presence of the propylene-based polymer component (1) produced in step (1) and the propylene-based copolymer component (2A) produced in step (2A), D sol This is the process for producing the propylene copolymer component (2B) of the propylene-ethylene copolymer rubber, which is the main component of the product.

[0075] The ethylene content in requirement (i) or (ii) can be adjusted by adjusting the ratio of ethylene feed to propylene feed during process (2A) or process (2B), respectively. In other words, increasing this ratio of feed will increase the ethylene content, and decreasing this ratio will decrease the ethylene content.

[0076] The intrinsic viscosity [η] in requirement (i) or (ii) can be adjusted by the amount of hydrogen gas used as a chain transfer agent during process (2A) or process (2B), respectively. In other words, the intrinsic viscosity [η] can be decreased by increasing the ratio of hydrogen gas feed to monomer feed, and the intrinsic viscosity [η] can be increased by decreasing the ratio of hydrogen gas feed to monomer feed.

[0077] The mass ratio (iii) of the propylene copolymer component (2A) to the propylene copolymer component (2B) in requirement (iii) can be adjusted, for example, by adjusting the polymerization time of each step. In other words, the mass ratio (iii) can be increased by increasing the proportion of the polymerization time of step (2A) to the total polymerization time. Conversely, the mass ratio (iii) can be decreased by increasing the proportion of the polymerization time of step (2B) to the total polymerization time.

[0078] The mass ratio (iv) of propylene polymer component (1) to propylene copolymer component (2A) and propylene copolymer component (2B) in requirement (iv) can be adjusted, for example, by adjusting the polymerization time of each step. In other words, the mass ratio (iv) can be increased by increasing the proportion of the polymerization time of step (1) to the total polymerization time. Conversely, the mass ratio (iv) can be decreased by increasing the proportion of the polymerization time of steps (2A) and (2B) to the total polymerization time.

[0079] Requirement (v), namely the MFR of the propylene-based block copolymer, can be adjusted by adjusting the ratio of hydrogen gas feed as a chain transfer agent to the amount of monomer feed (i.e., propylene in the case of propylene homopolymerization, and propylene and ethylene in the case of copolymerization) during steps (1) to (2B). In other words, increasing this ratio can increase the MFR, and decreasing this ratio can decrease the MFR.

[0080] Requirement (v), namely the melting point of the propylene-based block copolymer, can be adjusted by preparing the catalyst and external donor system used for polymerization. After polymerization is complete, post-treatment steps such as known catalyst deactivation steps, catalyst residue removal steps, and drying steps may be performed as needed.

[0081] [Propylene resin composition] The propylene-based resin composition according to the present invention is characterized by containing the propylene-based block copolymer according to the present invention described above.

[0082] (Inorganic filler (F)) The propylene-based resin composition of the present invention may further contain an inorganic filler (F) in addition to the propylene-based block copolymer of the present invention, from the viewpoint of improving rigidity, heat resistance, etc.

[0083] Examples of inorganic fillers (F) include talc, clay, calcium carbonate, mica, silicates, carbonates, glass fibers, and carbon fibers. Among these, talc and calcium carbonate are preferred, and talc is particularly preferred.

[0084] The average particle size of the talc should preferably be in the range of 1 to 5 μm, more preferably 1 to 3 μm. The inorganic filler (F) can be used alone or in combination of two or more types.

[0085] In relation to 100 parts by mass of the total amount of the propylene-based block copolymer of the present invention and the inorganic filler (F), the content of the inorganic filler (F) is 1 to 50 parts by mass, preferably 3 to 40 parts by mass, and more preferably 5 to 25 parts by mass. The content of the propylene-based block copolymer of the present invention is 50 to 99 parts by mass, preferably 60 to 97 parts by mass, and more preferably 75 to 95 parts by mass.

[0086] (Elastomer (E)) The propylene-based resin composition of the present invention may further contain an elastomer (E) in addition to the propylene-based block copolymer of the present invention, from the viewpoint of adjusting the molding shrinkage rate and imparting paintability.

[0087] Examples of elastomers (E) include ethylene-α-olefin random copolymers (Ea), ethylene-α-olefin-unconjugated polyene random copolymers (Eb), hydrogenated block copolymers (Ec), other elastic polymers, and mixtures thereof.

[0088] The content of elastomer (E) is typically 1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total of the propylene-based block copolymer and elastomer (E) of the present invention. The content of propylene-based block copolymer of the present invention is typically 50 to 99 parts by mass, preferably 70 to 99 parts by mass, and more preferably 85 to 99 parts by mass.

[0089] The ethylene-α-olefin random copolymer (Ea) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. These α-olefins can be used individually or in combination. Among these, propylene, 1-butene, 1-hexene, and 1-octene are particularly preferred.

[0090] The ethylene-α-olefin random copolymer (Ea) preferably has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of typically 95 / 5 to 70 / 30, preferably 90 / 10 to 75 / 25. The ethylene-α-olefin random copolymer (Ea) preferably has a MFR of 0.1 g / 10 min or more, preferably 0.5 to 5 g / 10 min, at 190°C and a load of 2.16 kg.

[0091] The ethylene-α-olefin-non-conjugated polyene random copolymer (Eb) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. The α-olefin having 3 to 20 carbon atoms is the same as described above. Examples of the aforementioned non-conjugated polyethylene include acyclic dienes such as 5-ethylidene-2-norbornene, 5-propyridene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and norbornadiene; chain-like non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene. Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferred.

[0092] The ethylene-α-olefin-non-conjugated polyene random copolymer (Eb) preferably has a molar ratio of ethylene, α-olefin, and non-conjugated polyene (ethylene / α-olefin / non-conjugated polyene) of 90 / 5 / 5 to 30 / 45 / 25, more preferably 80 / 10 / 10 to 40 / 40 / 20.

[0093] The ethylene-α-olefin-non-conjugated polyene random copolymer (Eb) should preferably have a MFR of 0.05 g / 10 min or more, more preferably 0.1 to 10 g / 10 min, at 190°C and a load of 2.16 kg. Specific examples of ethylene-α-olefin-non-conjugated polyene random copolymer (Eb) include ethylene-propylene-diene terpolymer (EPDM).

[0094] The hydrogenated block copolymer (Ec) is a hydrogenated block copolymer whose block form is represented by the following formula (a) or (b), and is a hydrogenated block copolymer with a hydrogenation rate of 90 mol% or more, preferably 95 mol% or more. X(YX)n ···(a) (XY)n ···(b)

[0095] In formula (a) or (b) above, X represents a monovinyl-substituted aromatic hydrocarbon, and Y represents a conjugated diene. n is an integer from 1 to 5, preferably 1 or 2.

[0096] Examples of monovinyl-substituted aromatic hydrocarbons constituting the polymerization block represented by X in formula (a) or (b) above include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, lower alkyl-substituted styrene, vinylnaphthalene, and other styrene or its derivatives. These can be used individually or in combination of two or more.

[0097] Examples of conjugated dienes that constitute the polymerization block represented by Y in formula (a) or (b) above include butadiene, isoprene, and chloroprene. These can be used individually or in combination of two or more.

[0098] Specific examples of hydrogenated block copolymers (Ec) include styrene-ethylene-butene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), and styrene-ethylene-propylene block copolymers (SEP), among other styrene-based block copolymers.

[0099] The propylene-based resin composition of the present invention may contain both the inorganic filler (F) and the elastomer (E) described above, along with the propylene-based block copolymer of the present invention, from the viewpoint of achieving a high balance of physical properties such as rigidity, heat resistance, improved dimensional accuracy, and paintability.

[0100] For a total of 100 parts by mass of the propylene-based block copolymer, elastomer (E), and inorganic filler (F) of the present invention, the propylene-based block copolymer is 50 to 98 parts by mass, preferably 60 to 98 parts by mass, more preferably 70 to 98 parts by mass; the elastomer (E) is 1 to 49 parts by mass, preferably 1 to 39 parts by mass, more preferably 1 to 29 parts by mass; and the inorganic filler (F) is 1 to 49 parts by mass, preferably 1 to 39 parts by mass, more preferably 1 to 29 parts by mass.

[0101] (Other additives) In addition to these components, the propylene resin composition of the present invention may also contain, as appropriate, additives such as neutralizing agents, antioxidants, heat stabilizers, weathering agents, lubricants, ultraviolet absorbers, antistatic agents, antiblocking agents, antifogging agents, anti-foaming agents, dispersants, flame retardants, antibacterial agents, fluorescent whitening agents, crosslinking agents, and crosslinking aids; and colorants such as dyes and pigments (hereinafter referred to as "other components").

[0102] If the propylene-based resin composition of the present invention contains other components, the amount of the other components is typically 0.01 to 5 parts by mass in total, per 100 parts by mass of the propylene-based block copolymer of the present invention.

[0103] The propylene resin composition of the present invention can be produced by conventionally known methods, such as melt-kneading each component in a kneader.

[0104] [Molded body] The molded article of the present invention is a molded article formed from the propylene-based block copolymer or propylene-based resin composition of the present invention described above.

[0105] Methods for molding the propylene-based block copolymer or propylene-based resin composition of the present invention include conventionally known methods such as injection molding, extrusion molding, hollow molding, film molding, sheet molding, foam molding, injection foam molding, stretch molding, injection stretch blow molding, vacuum molding, and press molding.

[0106] The molded articles of the present invention can be suitably used for automotive interior materials such as instrument panels and door panels, automotive exterior materials such as bumpers and fenders, and other components that require a balance between rigidity and impact resistance. They can also be suitably used in various fields such as home appliance parts, food containers, and medical containers. [Examples]

[0107] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0108] (Measurement method and evaluation method) (1) Polymer or polymer mixture: [MFR] The melt flow rate (MFR) was measured according to ASTM D-1238 (measurement temperature 230°C, load 2.16 kg).

[0109] [Intrinsic viscosity [η]] Approximately 25 mg of the sample was dissolved in 25 ml of tetralin, and the specific viscosity η was measured in an oil bath at 135°C. sp The specific viscosity η was measured. After diluting this tetralin solution by adding 5 ml of tetralin solvent, the specific viscosity η was measured in the same manner. sp The following was measured. This dilution procedure was repeated two more times, and the η obtained by extrapolating the concentration (C) to 0 was obtained. sp The value of / C was determined as the intrinsic viscosity, and this value was defined as the intrinsic viscosity [η].

[0110] [Percentage of ethylene-derived constituent units] Regarding the measurement sample, under the following conditions: 13 13C-NMR measurements were performed. ( 13 C-NMR measurement conditions) Measurement device: JEOL LA400 nuclear magnetic resonance spectrometer Measurement mode: BCM (Bilevel Complete decoupling) Observation frequency: 100.4MHz Observation range: 17006.8Hz Pulse width: 45° of the C nucleus (7.8 μsec) Pulse repetition time: 5 seconds Sample tube: 5mmφ Sample tube rotation speed: 12Hz Total number of times: 20,000 Measurement temperature: 125℃ Solvent: 1,2,4-Trichlorobenzene: 0.35 ml / Deuterated benzene: 0.2 ml Sample quantity: approximately 40 mg

[0111] From the spectra obtained by measurement, the ratio of monomer chain distributions (triad distributions) was determined in accordance with the following reference (1), and the mole fraction (mol%) of ethylene-derived constituent units (hereinafter referred to as E(mol%)) and the mole fraction (mol%) of propylene-derived constituent units (hereinafter referred to as P(mol%)) in the measurement sample were calculated. From the obtained E(mol%) and P(mol%), the proportion (mass%) of ethylene-derived constituent units (hereinafter referred to as E(mass%)) in the measurement sample was calculated according to the following formula (Equation 1).

[0112] Literature (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titanium trichloride-diethylaluminum chloride. Macromolecules 1982, 15, (4), 1150-1152 E(mass%)=E(mol%)×28×100 / [P(mol%)×42+E(mol%)×28](Formula 1)

[0113] [Melting point] In accordance with JIS K7121, measurements were performed using a differential scanning calorimeter (DSC, PerkinElmer (Diamond DSC)) under the following conditions, and the temperature at the peak of the endothermic peak in step 3 was defined as the melting point (Tm). If there were multiple endothermic peaks, the temperature at the peak of the largest endothermic peak was defined as the melting point (Tm).

[0114] (Measurement conditions) Atmosphere: Nitrogen gas atmosphere Sample amount: 5 mg Sample shape: Pressed film (molded at 230°C, thickness 200-400 μm) Step 1: Increase the temperature from 30°C to 240°C at a rate of 10°C / min, and hold for 10 minutes. Step 2: Cool the temperature down to 60°C at a rate of 10°C / minute. Step 3: Increase the temperature to 240°C at a rate of 10°C / min.

[0115] [Mesopentad fraction (mmmm fraction)] Mesopentad fraction (mmmm fraction, %), which is one of the indicators of stereoregularity of polymers and indicates their microtacticity, is a value determined by attribution based on Macromolecules 8,687 (1975) by A. Zambelli et al. for propylene homopolymers. 13 The mesopentade fraction was measured by 13C-NMR under the following conditions, and the mesopentade fraction was calculated as (peak area at 21.7 ppm) / (peak area at 19-23 ppm) × 100.

[0116] (Measurement conditions) Device: Bruker Iospin AVANCE III cryo-500 type nuclear magnetic resonance spectrometer Nucleus for measurement: 13 C(125MHz) Measurement mode: Single-pulse proton broadband decoupling Pulse width: 45° (5.00 microseconds) Repeat time: 5.5 seconds Total number of times: 256 Measurement solvent: o-dichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent Sample concentration: 50 mg / 0.6 mL Measurement temperature: 120℃ Chemical shift standard: 21.59 ppm

[0117] [Viscoelastic properties] Viscoelasticity measurements were performed using a sample prepared by compression molding 4g of the sample with a Φ45mm × 2mm spacer under the following conditions.

[0118] Compression molding machine: SFA-20H / C, manufactured by Shindo Metal Industries Co., Ltd. Molding temperature: 210℃ Cooling temperature: 30℃ Preheating time: 180 seconds Initial pressurization time: 10 seconds, Number of gas releases: 7 Secondary pressurization time: 60 seconds, molding pressure: 100 kgf / cm² 2 Cooling time: 180 seconds, Cooling pressure: 100 kgf / cm² 2

[0119] Equation (A) was determined by measuring the angular velocity [ω (rad / sec)] of the storage modulus (G') at a measurement temperature of 200°C in the range of 0.0101 ≤ ω ≤ 10¹. For the measurement, an Anton Paar Japan MCR301 rheometer was used, a parallel plate was used as the sample holder, and the sample thickness was set to approximately 1.0 mm. Five measurement points were taken for each digit of ω. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque within the measurement range could be detected without exceeding the torque limit.

[0120] [D insol The proportion and D sol [Percentage] 5 g of the sample was mixed with 200 ml of n-decane and heated at 145°C for 30 minutes to dissolve and obtain solution (1). Next, solution (1) was cooled to 23°C over approximately 2 hours, and then left to stand at 23°C for 30 minutes to obtain solution (2) containing precipitate (α). Subsequently, precipitate (α) was filtered from solution (2) using a filter cloth with a mesh size of approximately 15 μm, and after drying the precipitate (α), the mass of precipitate (α) was measured. The mass of precipitate (α) divided by the sample mass (5 g) was used to determine the 23°C n-decane insoluble portion (D insol ) was used as the ratio.

[0121] Furthermore, the solution (2) from which precipitate (α) was filtered was placed in approximately three times the volume of acetone to precipitate the components dissolved in n-decane, thereby obtaining precipitate (β). Subsequently, precipitate (β) was filtered using a glass filter (G2, mesh size approximately 100-160 μm), dried, and then the mass of precipitate (β) was measured. The mass of precipitate (β) divided by the sample mass (5 g) was used to determine the n-decane soluble portion at 23°C (D sol ) was used as the ratio.

[0122] (2) Evaluation of the molded product: [Flexural modulus] In accordance with JIS K7171, test specimens were prepared from the propylene-based block copolymer of the example and the polymer mixture of the comparative example, and the flexural modulus was measured under the following conditions.

[0123] Measurement conditions Test specimen: 10mm (width) x 80mm (length) x 4.0mm (thickness) Bending speed: 2 mm / min Bending span: 64mm

[0124] [Charpy impact strength] In accordance with JIS K7111, test specimens were prepared from the propylene-based block copolymer of the example and the polymer mixture of the comparative example, and the notched Charpy impact strength was measured under the following conditions.

[0125] Measurement conditions Temperature: -30°C and 23°C Test specimen: 10mm (width) x 80mm (length) x 4mm (thickness) The notch is a machining process.

[0126] [High-speed surface impact test] At -30°C, a load cell-equipped impinger with a 1 / 2-inch tip diameter was impacted at a speed of 5 m / s onto a 3 mm thick rectangular plate specimen. A support stand with a 3-inch tip diameter (receiving diameter) was used on the back of the specimen. The total absorbed energy (J) of the specimen was then determined.

[0127] [Spiral Flow] A mold for measuring resin flow length was used, which had a spiral-shaped channel with a thickness of 3 mm and a width of 10 mm. The measurement was performed under the spiral flow measurement injection molding conditions described below. Injection molding machine: J110AD, manufactured by Japan Steel Works Ltd. Cylinder temperature: 230℃ Mold temperature: 40℃ Injection time: 10 seconds (no holding pressure setting)

[0128] [Manufacturing Example 1] (Solid titanium catalyst component) According to the preparation of <Solid Titanium Catalyst Component (i-1)> in Production Example 3 of Japanese Patent Publication No. 2020-114909, a solid titanium catalyst component containing 1.3% by weight of titanium, 20% by weight of magnesium, 13.8% by weight of diisobutyl phthalate, and 0.8% by weight of diethyl phthalate was obtained.

[0129] [Manufacturing Example 2] (Preparation of prepolymerization catalyst) 112.0 g of the solid titanium catalyst component synthesized in Production Example 1, 83.0 mL of triethylaluminum, 23.6 mL of diethylaminotriethoxysilane, and 10 L of heptane were placed in a 20 L autoclave equipped with a stirrer. Maintaining an internal temperature of 15-20°C, 672 g of propylene was added, and the reaction was carried out with stirring for 120 minutes. After polymerization was complete, the solid component was allowed to settle, and the supernatant was removed and washed twice with heptane. The obtained prepolymerization catalyst was resuspended in purified heptane, and the concentration of the solid titanium catalyst component was adjusted by adding heptane to 0.7 g / L. This prepolymerization catalyst contained 6 g of polypropylene per gram.

[0130] [Example A1] (Production of propylene-based block copolymer (A-1)) <Process (1)> 300 L of propylene was charged into a 1000 L capacity vessel polymerizer equipped with a stirrer, and while maintaining this liquid level, 118 kg / h of propylene, 1.2 g / h of prepolymerization catalyst as a solid catalyst component, 13.3 mL / h of triethylaluminum, and 5.1 mL / h of diethylaminotriethoxysilane were continuously supplied. Polymerization was carried out at a temperature of 73.5 °C, a pressure of 3.39 MPa-G, and an average residence time of 1.1 hours. The resulting slurry was sent to a 500 L capacity vessel polymerizer equipped with a stirrer, and further polymerization was carried out. In the second polymerizer, 300 L of propylene was charged, and while maintaining this liquid level, 14.5 kg / h of propylene, 3.2 g / h of dicyclopentadienyldichlorotitanium, and hydrogen were continuously supplied so that the hydrogen concentration in the gas phase was 7.3 mol%. Polymerization was carried out at a temperature of 73.5°C, a pressure of 3.27 MPa-G, and an average residence time of 1.0 hour to obtain homopropylene polymer (H-1).

[0131] <Process (2A)> The obtained homopropylene polymer (H-1) slurry was sent to a 500L capacity vessel polymerizer with a stirrer (No. 3 polymerizer) for further polymerization. In No. 3 polymerizer, 260L of propylene was charged, and while maintaining this liquid level, propylene was supplied at a rate of 16.9 kg / h, ethoxyethoxyethyl acetate as an activity regulator at a rate of 0.28 ml / h, ethylene was supplied so that the concentration of ethylene dissolved in the propylene liquid phase was 0.198 mol per 1 mol of propylene, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.9 mol%. Polymerization was carried out at a temperature of 53.2°C, a pressure of 3.24 MPa-G, an average residence time of 0.75 hours, and an ethylene concentration in the gas phase of 29.1 mol% to obtain block copolymer (B-1).

[0132] <Process (2B)> The slurry of the obtained copolymer (B-1) was sent to a 500L vessel polymerizer (No. 4) equipped with a stirrer, where further polymerization was carried out. In the No. 4 polymerizer, 260L of propylene was charged, and while maintaining this liquid level, polymerization was carried out by continuously supplying propylene at a rate of 52.1 kg / h, dicyclopentadienyldichlorotitanium at a rate of 35.2 mg / h, and ethylene at a rate of 0.129 mol per mol of propylene, and hydrogen at a rate of 0.16 mol% in the gas phase. At this time, the temperature was 60.4°C, the pressure was 3.16 MPa-G, the average residence time was 0.55 hours, and the ethylene concentration in the gas phase was 19.7 mol%.

[0133] The obtained slurry was deactivated, vaporized, and then subjected to gas-solid separation, followed by vacuum drying at 80°C. This yielded a propylene-based block copolymer (A-1). The properties of the obtained homopropylene polymer (H-1), block copolymer (B-1), and propylene-based block copolymer (A-1) were as follows.

[0134] • Homopropylene polymer (H-1) Intrinsic viscosity [η]=0.78dl / g MFR (2.16kg load, 230℃) = 240g / 10min • Block copolymer (B-1) Intrinsic viscosity [η]=1.04dl / g MFR (2.16kg load, 230℃) = 127g / 10min Ethylene content = 13.0% by mass Percentage of n-decane soluble portion at 23°C = 16.7% by weight Ethylene content of the n-decane soluble portion at 23°C = 53.6 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 2.1 dl / g • Propylene-based block copolymer (A-1) Intrinsic viscosity [η]=1.39dl / g MFR (2.16kg load, 230℃) = 54g / 10min Ethylene content = 15.4% by mass Percentage of n-decane soluble portion at 23°C = 19.3% by weight Ethylene content of n-decane soluble portion at 23°C = 52.3 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 3.3 dl / g

[0135] Table 1 shows the physical properties of the propylene-based block copolymer (A-1), etc., determined based on these characteristics. Note that the propylene-based polymer component (1) was considered to be the 23°C n-decane insoluble portion, while the propylene-based copolymer components (2A) and (2B) were considered to be the 23°C n-decane soluble portion.

[0136] [Example A2] (Production of propylene-based block copolymer (A-2)) <Process (1)> 300 L of propylene was charged into a 1000 L capacity vessel polymerizer equipped with a stirrer. While maintaining this liquid level, 118 kg / h of propylene, 1.2 g / h of prepolymerization catalyst as a solid catalyst component, 17 mL / h of triethylaluminum, 6.8 mL / h of diethylaminotriethoxysilane, and 660 NL / h of hydrogen were continuously supplied to achieve a hydrogen concentration of 7.5 mol% in the gas phase. Polymerization was carried out at a temperature of 73°C, a pressure of 3.5 MPa-G, and an average residence time of 1.1 hours.

[0137] The obtained slurry was sent to a second polymerizer, a vessel equipped with a stirrer with a capacity of 500 L, and further polymerization was carried out. In the second polymerizer, 300 L of propylene was charged, and while maintaining this liquid level, propylene was continuously supplied at a rate of 15 kg / h, dicyclopentadienyldichlorotitanium at a rate of 3.2 g / h, and hydrogen at a rate of 350 NL / h so that the hydrogen concentration in the gas phase was 8.1 mol%. Polymerization was carried out at a temperature of 73°C, a pressure of 3.4 MPa-G, and an average residence time of 1.0 hour to obtain homopropylene polymer (H-2).

[0138] <Process (2A)> The obtained homopropylene polymer (H-2) slurry was sent to a 500L vessel polymerizer equipped with a stirrer, and further polymerization was carried out. In the third polymerizer, 260L of propylene was charged, and while maintaining this liquid level, propylene was continuously supplied at a rate of 17 kg / h, ethoxyethoxyethyl acetate as an activity regulator at a rate of 0.46 ml / h, ethylene at a rate of 19 kg / h, and hydrogen at a rate of 380 NL / h so that the hydrogen concentration in the gas phase was 6.0 mol%. Polymerization was carried out at a temperature of 53°C, a pressure of 3.2 MPa-G, an average residence time of 0.75 hours, and an ethylene concentration in the gas phase of 29.0 mol%, to obtain block copolymer (B-2).

[0139] <Process (2B)> The resulting copolymer slurry was sent to a 500L capacity vessel polymerizer (No. 4) equipped with a stirrer for further polymerization. In the No. 4 polymerizer, 260L of propylene was charged, and while maintaining this liquid level, polymerization was carried out by continuously supplying 52 kg / h of propylene, 25 mg / h of dicyclopentadienyldichlorotitanium, 0.49 kg / h of ethylene, and 23 NL / h of hydrogen so that the hydrogen concentration in the gas phase was 0.17 mol%. At this time, the temperature was 60°C, the pressure was 3.2 MPa-G, the average residence time was 0.55 hours, and the ethylene concentration in the gas phase was 19.2 mol%.

[0140] The obtained slurry was deactivated, vaporized, and then subjected to gas-solid separation, followed by vacuum drying at 80°C. This yielded a propylene-based block copolymer (A-2). The properties of the obtained homopropylene polymer (H-2), block copolymer (B-2), and propylene-based block copolymer (A-2) were as follows.

[0141] • Homopropylene polymer (H-2) Intrinsic viscosity [η]=0.78dl / g MFR (2.16kg load, 230℃) = 250g / 10min Mesopentadol fraction (mmmm fraction) = 98.1 mol% • Block copolymer (B-2) Intrinsic viscosity [η]=0.89dl / g MFR (2.16kg load, 230℃) = 162g / 10min Ethylene content = 10.1% by mass Percentage of n-decane soluble portion at 23°C = 11.5% by mass Ethylene content of n-decane soluble portion at 23℃ = 54 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 2.0 dl / g • Propylene-based block copolymer (A-2) Intrinsic viscosity [η]=1.23dl / g MFR (2.16kg load, 230℃) = 95g / 10min Ethylene content = 11.8% by mass Percentage of n-decane soluble portion at 23°C = 14% by mass Ethylene content of n-decane soluble portion at 23℃ = 52 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 2.8 dl / g

[0142] Table 1 shows the properties of the propylene-based block copolymer (A-2), etc., determined based on these characteristics. Note that the propylene-based polymer component (1) was considered to be the 23°C n-decane insoluble portion, while the propylene-based copolymer components (2A) and (2B) were considered to be the 23°C n-decane soluble portion.

[0143] [Example A3] (Production of propylene-based block copolymer (A-3)) <Process (1)> 300 L of propylene was charged into a 1000 L capacity vessel polymerizer equipped with a stirrer. While maintaining this liquid level, 118 kg / h of propylene, 1.2 g / h of prepolymerization catalyst as a solid catalyst component, 17 mL / h of triethylaluminum, 6.8 mL / h of diethylaminotriethoxysilane, and 641 NL / h of hydrogen were continuously supplied to achieve a hydrogen concentration of 7.1 mol% in the gas phase. Polymerization was carried out at a temperature of 73°C, a pressure of 3.5 MPa-G, and an average residence time of 1.1 hours.

[0144] The obtained slurry was sent to a second polymerizer, a vessel equipped with a stirrer with a capacity of 500 L, and further polymerization was carried out. In the second polymerizer, 300 L of propylene was charged, and while maintaining this liquid level, propylene was continuously supplied at a rate of 15 kg / h, dicyclopentadienyldichlorotitanium at a rate of 3.1 g / h, and hydrogen at a rate of 345 NL / h so that the hydrogen concentration in the gas phase was 8.9 mol%. Polymerization was carried out at a temperature of 73°C, a pressure of 3.4 MPa-G, and an average residence time of 1.0 hour to obtain homopropylene polymer (H-3).

[0145] <Process (2A)> The obtained homopropylene polymer (H-3) slurry was sent to a 500L capacity vessel polymerizer with a stirrer (No. 3 polymerizer) for further polymerization. In the No. 3 polymerizer, 260L of propylene was charged, and while maintaining this liquid level, propylene was continuously supplied at a rate of 17 kg / h, ethoxyethoxyethyl acetate as an activity regulator at 0.40 ml / h, ethylene at 20 kg / h, and hydrogen at a rate of 300 NL / h to achieve a hydrogen concentration of 5.9 mol% in the gas phase. Polymerization was carried out at a temperature of 53°C, a pressure of 3.2 MPa-G, an average residence time of 0.74 hours, and an ethylene concentration of 28.9 mol% in the gas phase to obtain block copolymer (B-3).

[0146] <Process (2B)> The resulting copolymer slurry was sent to a 500L capacity vessel polymerizer (No. 4) equipped with a stirrer for further polymerization. In the No. 4 polymerizer, 260L of propylene was charged, and while maintaining this liquid level, polymerization was carried out by continuously supplying 52 kg / h of propylene, 25 mg / h of dicyclopentadienyldichlorotitanium, 0.59 kg / h of ethylene, and 24 NL / h of hydrogen so that the hydrogen concentration in the gas phase was 0.20 mol%. At this time, the temperature was 60°C, the pressure was 3.2 MPa-G, the average residence time was 0.55 hours, and the ethylene concentration in the gas phase was 20.0 mol%.

[0147] The obtained slurry was deactivated, vaporized, and then subjected to gas-solid separation, followed by vacuum drying at 80°C. This yielded a propylene-based block copolymer (A-3). The properties of the obtained homopropylene polymer (H-3), block copolymer (B-3), and propylene-based block copolymer (A-3) were as follows.

[0148] • Homopropylene polymer (H-3) Intrinsic viscosity [η]=0.78dl / g MFR (2.16kg load, 230℃) = 240g / 10min Mesopentadol fraction (mmmm fraction) = 98.1 mol% • Block copolymer (B-3) Intrinsic viscosity [η]=0.89dl / g MFR (2.16kg load, 230℃) = 144g / 10min Ethylene content = 11.6% by mass Percentage of n-decane soluble portion at 23°C = 14.1% by weight Ethylene content of n-decane soluble portion at 23℃ = 54 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 2.1 dl / g • Propylene-based block copolymer (A-3) Intrinsic viscosity [η]=1.10dl / g MFR (2.16kg load, 230℃) = 76g / 10min Ethylene content = 13.5% by mass Percentage of n-decane soluble portion at 23°C = 17% by weight Ethylene content of n-decane soluble portion at 23℃ = 53 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 3.1 dl / g

[0149] Table 1 shows the properties of the propylene-based block copolymer (A-3) and other components determined based on these characteristics. Note that propylene-based polymer component (1) was considered to be the 23°C n-decane insoluble portion, while propylene-based copolymer components (2A) and (2B) were considered to be the 23°C n-decane soluble portion.

[0150] [Polymer Production Example 1] (Production of polymers for blending (block copolymer (a-1))) A tubular polymerization reactor with a capacity of 8 L was continuously supplied with 20 kg / h of propylene, 0.5 NL / h of hydrogen, 0.38 g / h of prepolymerization catalyst per solid catalyst component, 2.1 mL / h of triethylaluminum, and 1.6 mL / h of diethylaminotriethoxysilane, and polymerization was carried out in a completely liquid state without a gas phase. The temperature of the tubular polymerization reactor was 16°C and the pressure was 3.6 MPa-G.

[0151] The obtained slurry was sent to a tubular polymerizer with a capacity of 58 L for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 23 kg / h and hydrogen at a rate of 172 NL / h, at a temperature of 70°C, a pressure of 3.6 MPa-G, and an average residence time of 0.61 hours. The obtained slurry was sent to a vessel polymerizer with a stirrer with a capacity of 70 L for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 45 kg / h and hydrogen was continuously supplied so that the hydrogen concentration in the gas phase was 9.6 mol%. Polymerization was carried out at a temperature of 68.0°C, a pressure of 3.2 MPa-G, and an average residence time of 0.35 hours to obtain homopropylene polymer (h-1).

[0152] The obtained slurry was transferred to a 2.4 L transfer tube, and in the transfer tube, an activity regulator (Atomer 163, manufactured by Croda Japan Co., Ltd.) was supplied at a rate of 1.83 g / h and an anti-adhesion agent (L-71 (trade name), manufactured by ADEKA Corporation) was supplied at a rate of 0.51 g / h, bringing the slurry into contact with the solvent. The slurry that had come into contact with the solvent was gasified, and after gas-solid separation was performed, 12.4 kg of homopropylene polymer (h-1) powder was sent to a 480 L gas-phase polymerizer. Then, propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerizer so that the gas composition was ethylene / (ethylene + propylene) = 0.3295 (molar ratio) and hydrogen / ethylene = 0.1460 (molar ratio). Polymerization was carried out at a temperature of 70°C, a pressure of 1.2 MPa-G, and a residence time of 0.68 hours.

[0153] Subsequently, gas-solid separation was performed, and the mixture was vacuum-dried at 80°C to obtain block copolymer (a-1). The properties of the obtained homopropylene (h-1) and block copolymer (a-1) were as follows.

[0154] • Homopropylene polymer (h-1) Intrinsic viscosity [η]=0.74dl / g MFR (2.16kg load, 230℃) = 252g / 10min Mesopentadione fraction (mmmm fraction) = 98.2 mol% • Block copolymer (a-1) Intrinsic viscosity [η]=0.94dl / g MFR (2.16kg load, 230℃) = 90g / 10min Ethylene content = 15.1% by mass Percentage of n-decane soluble portion at 23°C = 19.5% by mass Ethylene content of n-decane soluble portion at 23℃ = 53 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 2.1 dl / g

[0155] [Example of Polymer Production 2] (Production of polymers for blending (block copolymer (a-2))) A tubular polymerizer with a capacity of 8 L was continuously supplied with 20 kg / h of propylene, 0.5 NL / h of hydrogen, 0.30 g / h of prepolymerization catalyst per solid catalyst component, 1.7 mL / h of triethylaluminum, and 1.3 mL / h of diethylaminotriethoxysilane, and polymerization was carried out in a completely liquid state without a gas phase. The temperature of the tubular polymerizer was 16°C and the pressure was 3.2 MPa-G. The resulting slurry was sent to a tubular polymerizer with a capacity of 58 L for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 23 kg / h and hydrogen at a rate of 172 NL / h, the temperature was 63°C, the pressure was 3.2 MPa-G, and the average residence time was 0.60 hours.

[0156] The obtained slurry was sent to a 70L vessel polymerizer equipped with a stirrer for further polymerization. Propylene was supplied to the polymerizer at a rate of 45 kg / h, and hydrogen was continuously supplied to maintain a hydrogen concentration of 9.5 mol% in the gas phase. Polymerization was carried out at a temperature of 62.0°C, a pressure of 2.8 MPa-G, and an average residence time of 0.35 hours to obtain homopropylene polymer (h-2).

[0157] The obtained slurry was transferred to a 2.4 L transfer tube, and an anti-fouling agent (L-71 (product name), manufactured by ADEKA Corporation) was supplied at a rate of 0.32 g / h within the transfer tube and brought into contact with the slurry. The slurry that came into contact with the slurry was gasified, and after gas-solid separation was performed, homopropylene polymer (h-2) powder was sent to a 480 L gas-phase polymerizer so that the powder volume was 20.6 kg. Then, propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas-phase polymerizer was ethylene / (ethylene + propylene) = 0.1465 (molar ratio) and hydrogen / ethylene = 0.0030 (molar ratio). Polymerization was carried out at a polymerization temperature of 75°C, a pressure of 1.6 MPa-G, and a residence time of 1.42 hours.

[0158] Subsequently, gas-solid separation was performed, and the mixture was vacuum-dried at 80°C to obtain block copolymer (a-2). The properties of the obtained homopropylene polymer (h-2) and block copolymer (a-2) were as follows.

[0159] • Homopropylene polymer (H-2) Intrinsic viscosity [η]=0.77dl / g MFR (2.16kg load, 230℃) = 250g / 10min Mesopentadione fraction (mmmm fraction) = 98.2 mol% • Block copolymer (a-2) Intrinsic viscosity [η]=4.06dl / g MFR (2.16kg load, 230℃) = 0.8g / 10min Ethylene content = 23.8% by mass Percentage of n-decane soluble portion at 23°C = 39.7% by mass Ethylene content of n-decane soluble portion at 23℃ = 45 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 8.0 dl / g

[0160] [Polymer Production Example 3] (Production of polymers for blending (block copolymer (a-3))) A tubular polymerization reactor with a capacity of 8 L was continuously supplied with 20 kg / h of propylene, 1.0 NL / h of hydrogen, 0.39 g / h of prepolymerization catalyst per solid catalyst component, 2.2 mL / h of triethylaluminum, and 1.7 mL / h of diethylaminotriethoxysilane, and polymerization was carried out in a completely liquid state without a gas phase. The temperature of the tubular polymerization reactor was 20°C and the pressure was 3.5 MPa-G.

[0161] The resulting slurry was sent to a tubular polymerizer with a capacity of 58 L for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 23 kg / h and hydrogen at a rate of 176 NL / h, at a temperature of 70°C, a pressure of 3.5 MPa-G, and an average residence time of 0.60 hours.

[0162] The obtained slurry was sent to a 70L vessel polymerizer equipped with a stirrer for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 45 kg / h, and hydrogen was supplied at a rate of 382 NL / h to achieve a hydrogen concentration of 9.6 mol% in the gas phase. Polymerization was carried out at a temperature of 67°C, a pressure of 3.1 MPa-G, and an average residence time of 0.36 hours to obtain homopropylene polymer (h-3).

[0163] The obtained slurry was transferred to a pipette with an internal volume of 2.4 L, and an anti-adhesion agent (L-71 (trade name), manufactured by ADEKA Corporation) was supplied at 0.60 g / h in the transfer pipe and brought into contact with the slurry. The contacted slurry was gasified, and after gas-solid separation, powder of a homopolypropylene polymer (h-3) was fed into a gas-phase polymerization reactor with an internal volume of 480 L so that the powder amount became 10 kg. Then, propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas-phase polymerization reactor became ethylene / (ethylene + propylene) = 0.321 (molar ratio) and hydrogen / ethylene = 0.168 (molar ratio), and polymerization was carried out at a temperature of 70°C, a pressure of 1.2 MPa-G, and a residence time of 0.56 hours.

[0164] Thereafter, gas-solid separation was carried out, and vacuum drying was carried out at 80°C to obtain a block copolymer (a-3). The properties of the obtained homopolypropylene (h-3) and block copolymer (a-3) were as follows.

[0165] · Homopolypropylene polymer (h-3) Limiting viscosity [η] = 0.74 dl / g MFR (2.16 kg load, 230°C) = 252 g / 10 min Meso pentad fraction (mmmm fraction) = 98.2 mol% · Block copolymer (a-3) Limiting viscosity [η] = 0.92 dl / g MFR (2.16 kg load, 230°C) = 137 g / 10 min Ethylene content = 11.3 mass% Ratio of 23°C n-decane soluble part = 15.9 mass% Ethylene content of 23°C n-decane soluble part = 53 mol% Limiting viscosity [η] of 23°C n-decane soluble part = 2.1 dl / g

[0166] [Polymer Production Example 4] (Production of polymer for blending (block copolymer (a-4))) Into a tubular polymerization reactor with an internal volume of 58 L, propylene was continuously fed at 23 kg / h, a prepolymerization catalyst at 0.30 g / h per solid catalyst component, triethylaluminum at 1.6 mL / h, diethylaminotriethoxysilane at 1.2 mL / h, and hydrogen at 246 NL / h. The temperature was 63 °C, the pressure was 3.5 MPa-G, and the average residence time was 0.60 hours.

[0167] The resulting slurry was sent to a stirred vessel polymerization reactor with an internal volume of 70 L for further polymerization. Into the polymerization reactor, propylene was continuously fed at 45 kg / h and hydrogen at 515 NL / h so that the hydrogen concentration in the gas phase was 15 mol%. Polymerization was carried out at a temperature of 62 °C, a pressure of 3.1 MPa-G, and an average residence time of 0.35 hours to obtain a homopolypropylene polymer (h-4).

[0168] The resulting slurry was transferred to a transfer pipe with an internal volume of 2.4 L, and an anti-adhesion agent (L-71 (trade name), manufactured by ADEKA Corporation) was supplied at 0.32 g / h in the transfer pipe and brought into contact with the slurry. The contacted slurry was gasified and gas-solid separation was performed. Then, the powder of the homopolypropylene polymer (h-4) was sent to a gas-phase polymerization reactor with an internal volume of 480 L so that the powder amount was 24 kg. Thereafter, propylene, ethylene, and hydrogen were continuously fed so that the gas composition in the gas-phase polymerization reactor was ethylene / (ethylene + propylene) = 0.115 (molar ratio) and hydrogen / ethylene = 0.00280 (molar ratio). Polymerization was carried out at a temperature of 75 °C, a pressure of 1.6 MPa-G, and a residence time of 1.4 hours.

[0169] Thereafter, gas-solid separation was performed and vacuum drying was carried out at 80 °C to obtain a block copolymer (a-4). The properties of the obtained homopolypropylene (h-4) and block copolymer (a-4) were as follows.

[0170] · Homopolypropylene polymer (h-4) Limiting viscosity [η] = 0.66 dl / g MFR (2.16 kg load, 230 °C) = 436 g / ten minutes Meso pentad fraction (mmmm fraction) = 97.3 mol% • Block copolymer (a-4) Intrinsic viscosity [η]=5.28dl / g MFR (2.16kg load, 230℃) = 1.2g / 10min Ethylene content = 20.5% by mass Percentage of n-decane soluble portion at 23°C = 40.0% by mass Ethylene content of n-decane soluble portion at 23℃ = 40 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 7.9 dl / g

[0171] [Polymerization Production Example 5] (Production of polymers for blending (block copolymer (a-5))) A tubular polymerization reactor with a capacity of 8 L was continuously supplied with 20 kg / h of propylene, 1.0 NL / h of hydrogen, 0.30 g / h of prepolymerization catalyst per solid catalyst component, 1.7 mL / h of triethylaluminum, and 1.3 mL / h of diethylaminotriethoxysilane, and polymerization was carried out in a completely liquid state without a gas phase. The temperature of the tubular polymerization reactor was 20°C and the pressure was 3.5 MPa-G.

[0172] The resulting slurry was sent to a tubular polymerizer with a capacity of 58 L for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 23 kg / h and hydrogen at a rate of 172 NL / h, at a temperature of 63°C, a pressure of 3.2 MPa-G, and an average residence time of 0.60 hours.

[0173] The obtained slurry was sent to a 70L vessel polymerizer equipped with a stirrer for further polymerization. Propylene was continuously supplied to the polymerizer at a rate of 45 kg / h, and hydrogen was supplied to maintain a hydrogen concentration of 9.5 mol% in the gas phase. Polymerization was carried out at a temperature of 62°C, a pressure of 2.8 MPa-G, and an average residence time of 0.35 hours to obtain homopropylene polymer (h-5).

[0174] The obtained slurry was transferred to a 2.4 L transfer tube, and an anti-fouling agent (L-71 (product name), manufactured by ADEKA Corporation) was supplied at a rate of 0.32 g / h within the transfer tube and brought into contact with the slurry. The slurry that had come into contact with the slurry was gasified and gas-solid separation was performed. Then, 19 kg of homopropylene polymer (h-5) powder was sent to a 480 L gas-phase polymerizer. Subsequently, propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerizer so that the gas composition was ethylene / (ethylene + propylene) = 0.166 (molar ratio) and hydrogen / ethylene = 0.00293 (molar ratio). Polymerization was carried out at a temperature of 75°C, a pressure of 1.6 MPa-G, and a residence time of 1.3 hours.

[0175] Subsequently, gas-solid separation was performed, and the mixture was vacuum-dried at 80°C to obtain block copolymer (a-5). The properties of the obtained homopropylene (h-5) and block copolymer (a-5) were as follows.

[0176] • Homopropylene polymer (h-5) Intrinsic viscosity [η]=0.77dl / g MFR (2.16kg load, 230℃) = 250g / 10min Mesopentadione fraction (mmmm fraction) = 98.2 mol% • Block copolymer (a-5) Intrinsic viscosity [η]=4.15dl / g MFR (2.16kg load, 230℃) = 0.80g / 10min Ethylene content = 26.2% by mass Percentage of n-decane soluble portion at 23°C = 39.5% by mass Ethylene content of n-decane soluble portion at 23℃ = 46 mol% Intrinsic viscosity [η] of the n-decane soluble portion at 23℃ = 8.1 dl / g

[0177] [Comparative Example A1] (Production of polymer mixture (A'-1)) 83 parts by mass of block copolymer (a-1) produced in Polymer Production Example 1, 7.8 parts by mass of block copolymer (a-2) produced in Polymer Production Example 2, 9.2 parts by mass of homopropylene polymer (Prime Polypropylene® J137G (product name), manufactured by Prime Polymer Co., Ltd.), 0.1 parts by mass of calcium stearate (manufactured by NOF Corporation), and as antioxidants, 0.1 parts by mass of IRGANOX® 1010 (manufactured by BASF Japan Ltd.), 0.1 parts by mass of IRGAFOS 168 (manufactured by BASF Japan Ltd.), and 0.1 parts by mass of H-BHT (manufactured by Honshu Chemical Industry Co., Ltd.) were blended and dry-blended in a tumbler mixer. Subsequently, the mixture was melt-kneaded using a twin-screw extruder (manufactured by Nakatani Machinery Co., Ltd.: NR-II, co-rotating twin-screw extruder) under the conditions of a barrel temperature (kneading temperature) of 190°C, a screw rotation speed of 200 rpm, and an extrusion rate of 20 kg / h to obtain polymer mixture (A'-1). The physical properties of polymer mixture (A'-1) are shown in Table 1.

[0178] [Comparative example A2] (Production of polymer mixture (A'-2)) Polymer mixture (A'-2) was obtained in the same manner as in Comparative Example 1, except that 75 parts by mass of block copolymer (a-3) produced in Polymer Production Example 3 and 5.4 parts by mass of block copolymer (a-4) produced in Polymer Production Example 4 were added instead of block copolymer (a-1) and block copolymer (a-2), and the amount of homopropylene polymer (Prime PolyPro J137G) was changed to 19.6 parts by mass. The physical properties of polymer mixture (A'-2) are shown in Table 1.

[0179] [Comparative example A3] (Production of polymer mixture (A'-3)) Polymer mixture (A'-3) was obtained in the same manner as in Comparative Example 1, except that 88.3 parts by mass of block copolymer (a-3) produced in Polymer Production Example 5 and 6 parts by mass of block copolymer (a-5) produced in Polymer Production Example 5 were added instead of block copolymer (a-1) and block copolymer (a-2), and the amount of homopropylene polymer (Prime PolyPro J137G) was changed to 5.7 parts by mass. The physical properties of polymer mixture (A'-3) are shown in Table 1.

[0180] [Table 1]

[0181] (Manufacture of Composition) [Example B1] 62 parts by mass of the propylene block copolymer (A-1) produced in Example A1, 17 parts by mass of an ethylene·1-butene copolymer (Tafmer (registered trademark) A-1050S (trade name), manufactured by Mitsui Chemicals, Inc.), 21 parts by mass of talc (JM-209 (trade name), manufactured by Asada Flour Milling Co., Ltd.), 0.1 part by mass of calcium stearate (manufactured by NOF Corporation), and 0.1 part by mass of IRGANOX 1010 (trade name, manufactured by BASF Japan Ltd.) and 0.1 part by mass of IRGAFOS 168 (trade name, manufactured by BASF Japan Ltd.) as antioxidants were blended by dry blending using a tumbler mixer. Then, it was melt-kneaded and pelletized under the conditions of a cylinder temperature of 180°C, a screw rotation speed of 750 rpm, and an extrusion rate of 60 kg / h using a twin-screw extruder (TEX (registered trademark) 30α, manufactured by Japan Steel Works, Ltd.). These pellets were molded into test pieces using an injection molding machine, and the above evaluation was performed. The results are shown in Table 2.

[0182] [Example B2] A composition was produced and evaluated in the same manner as in Example B1, except that the amount of the propylene block copolymer (A-1) was changed to 69 parts by mass and the amount of the ethylene·1-butene copolymer was changed to 10 parts by mass. The evaluation results are shown in Table 2.

[0183] [Example B3]<U+ A composition was produced and evaluated in the same manner as in Example B1, except that 62 parts by mass of the propylene block copolymer (A-1) was changed to 61 parts by mass of the propylene block copolymer (A-2) and the amount of the ethylene·1-butene copolymer was changed to 18 parts by mass. The evaluation results are shown in Table 2.

[0184] [Example B4] The composition was prepared and evaluated in the same manner as in Example B1, except that 62 parts by mass of propylene-based block copolymer (A-1) was replaced with 60 parts by mass of propylene-based block copolymer (A-3), and the amount of ethylene-1-butene copolymer was changed to 19 parts by mass. The evaluation results are shown in Table 2.

[0185] [Example B5] The composition was prepared and evaluated in the same manner as in Example B4, except that the amount of propylene-based block copolymer (A-3) was changed to 67 parts by mass and the amount of ethylene-1-butene copolymer was changed to 12 parts by mass. The evaluation results are shown in Table 2.

[0186] [Comparative Example B1] The composition was prepared and evaluated in the same manner as in Example B1, except that 62 parts by mass of propylene-based block copolymer (A-1) was replaced with 62 parts by mass of polymer mixture (A'-1). The evaluation results are shown in Table 2.

[0187] [Comparative example B2] The composition was prepared and evaluated in the same manner as in Comparative Example B1, except that the amount of polymer mixture (A'-1) was changed to 69 parts by mass and the amount of ethylene-1-butene copolymer was changed to 10 parts by mass. The evaluation results are shown in Table 2.

[0188] [Comparative Example B3] The composition was prepared and evaluated in the same manner as in Example B3, except that 61 parts by mass of propylene-based block copolymer (A-2) was replaced with 61 parts by mass of polymer mixture (A'-2). The evaluation results are shown in Table 2.

[0189] [Comparative example B4] The composition was prepared and evaluated in the same manner as in Example B4, except that 60 parts by mass of propylene-based block copolymer (A-3) was replaced with 60 parts by mass of polymer mixture (A'-3). The evaluation results are shown in Table 2.

[0190] [Comparative Example B5] The composition was prepared and evaluated in the same manner as in Comparative Example B4, except that the amount of polymer mixture (A'-3) was changed to 67 parts by mass and the amount of ethylene-1-butene copolymer was changed to 12 parts by mass. The evaluation results are shown in Table 2.

[0191] [Table 2]

Claims

1. A propylene-based block copolymer that satisfies the following requirements (1) to (4). Requirement (1): The soluble portion at 23°C n-decane is 10 to 50% by mass, the intrinsic viscosity [η] of the soluble portion at 23°C n-decane, measured in tetralin at 135°C, is 2.0 to 6.0 dl / g, and the ethylene content of the soluble portion at 23°C n-decane is 30 to 55 mol%. Requirement (2): The melt flow rate (230°C, 2.16 kg load) is 1 to 500 g / 10 min. Requirement (3): The melting point measured by a differential scanning calorimetry is 155 to 170°C. Requirement (4): In viscoelasticity measurements, the storage modulus is 10 2 Pa, 10 4 Let ω1 and ω2 be the angular frequencies (rad / s) at which Pa occurs, respectively. If α is the product of the amount of n-decane soluble at 23°C (mass%) and the intrinsic viscosity (dl / g) of the n-decane soluble at 23°C, then both equations (B) and (C) below are satisfied in the log-log plot of equation (A) - α below. ω2 / 10ω1 …(A) 5.88×ln(α)−21.1<ln(Formula (A))<5.88×ln(α)−17.8…(B) 2≦ln(formula (A))≦6…(C)

2. Furthermore, the propylene-based block copolymer according to claim 1 satisfies the following requirements (5) to (6). Requirement (5): Insoluble portion of n-decane at 23°C 13 The mesopentad fraction (mmmm fraction) measured by 13C-NMR is 96.0–99.9%. Requirement (6): The melt flow rate of the n-decane-insoluble portion at 23°C (230°C, 2.16 kg load) is 50 to 1000 g / 10 min.

3. A propylene resin composition containing the propylene block copolymer described in claim 1 or 2.

4. The propylene resin composition according to claim 3, further containing an inorganic filler (F).

5. 50 to 99 parts by mass of the propylene-based block copolymer according to claim 1 or 2, and The inorganic filler (F) is 1 to 50 parts by mass (provided that the total amount of the propylene-based block copolymer and the inorganic filler (F) is 100 parts by mass). A propylene-based resin composition according to claim 4, comprising the specified material.

6. The propylene resin composition according to claim 3, further containing an elastomer (E).

7. 50 to 99 parts by mass of the propylene-based block copolymer according to claim 1 or 2, and The elastomer (E) is 1 to 50 parts by mass (provided that the total amount of the propylene-based block copolymer and elastomer (E) is 100 parts by mass). A propylene-based resin composition according to claim 6, comprising the specified material.

8. 50 to 98 parts by mass of the propylene-based block copolymer according to claim 1 or 2, Inorganic filler (F) in 1 to 49 parts by mass, and Elastomer (E) 1 to 49 parts by mass (provided that the total amount of propylene-based block copolymer, inorganic filler (F), and elastomer (E) is 100 parts by mass). A propylene-based resin composition containing this resin.

9. A molded article formed from a propylene-based block copolymer according to claim 1 or 2, or from a propylene-based resin composition according to any one of claims 3 to 8.

10. The molded article according to claim 9, which is an injection-molded article.

11. A molded body according to claim 9 or 10, which is an automobile part.

Images