Propylene resin composition, molded article, and container

Abstract

The invention provides a propylene-based resin composition, and a molded article and a container formed from the composition. The propylene resin composition contains 40-85 parts by mass of a propylene polymer (A) that satisfies requirements (A1)-(A5), 5-30 parts by mass of an ethylene / alpha-olefin copolymer (B) that satisfies requirements (B2) and (B3), and 0-30 parts by mass of a polymer (C) that is at least one of a propylene homopolymer and a propylene / alpha-olefin random copolymer (provided that the total content of (A), (B), and (C) is 100 parts by mass). The content of the barium sulfate is 5-10 parts by mass, the content of the talc is 1-5 parts by mass, and the content of the nucleating agent is 0.1-0.6 parts by mass per 100 parts by mass of the total content of (A), (B), and (C). The details of the elements are shown in the specification.

Description

Technical Field

[0001] This invention relates to acrylic resin compositions, molded articles, and containers. Background Technology

[0002] For molded bodies used in residential facilities such as washbasins, air conditioners, humidifiers, toilet seats, and television casings, a certain degree of gloss and weight has always been required. The raw materials used for these molded bodies are primarily ABS (acrylonitrile / butadiene / styrene) resin or PS (polystyrene) resin, with a specific gravity of 1000 or higher.

[0003] In recent years, with the issue of reducing the environmental impact of plastics receiving global attention, the development of raw materials with lower proportions has become a demand, aiming to reduce resin emissions and lower costs.

[0004] For example, Patent Document 1 discloses a polypropylene resin composition that can produce molded articles with excellent mechanical strength such as flexural modulus and impact resistance, high heat distortion temperature and excellent surface properties. The polypropylene resin composition includes a polypropylene resin composed of propylene homopolymer and ethylene-propylene block copolymer, barium sulfate powder with an average particle size of 0.04 to 0.7 μm and a nucleating agent.

[0005] In addition, for example, Patent Document 2 discloses a polyolefin composition containing an inorganic filler, which can produce molded articles with improved tensile elongation and impact resistance without impairing the rigidity, heat resistance and dimensional stability of the molded article after it is made. The polyolefin composition containing an inorganic filler contains specific amounts of an inorganic filler, a cyclic phosphorus compound with a specific structure and a metal salt of a cyclic phosphorus compound with a specific structure in a crystalline polyolefin.

[0006] For example, Patent Document 3 discloses an propylene resin composition that, when used to manufacture molded bodies such as food packaging containers, achieves excellent rigidity, low-temperature impact resistance, and transparency even with thinner walls and lighter weight than existing technologies. This propylene resin composition contains a specific propylene polymer, a specific ethylene / α-olefin copolymer, and a nucleating agent.

[0007] Furthermore, for example, Patent Document 4 discloses an acrylic resin composition that can form a container that combines impact resistance and transparency for refrigeration purposes even when made into thin-walled, lightweight products, without compromising high-speed molding performance. This acrylic resin composition contains 82 to 92 parts by mass of an acrylic polymer (A) that meets specific requirements, 8 to 18 parts by mass of an ethylene / α-olefin copolymer (B) that meets specific requirements (wherein, the total of the acrylic polymer (A) and the ethylene / α-olefin copolymer (B) is set to 100 parts by mass), and 0.1 to 0.6 parts by mass of a nucleating agent (D).

[0008] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 5-295190 Patent Document 2: Japanese Patent No. 2906181 Patent Document 3: Japanese Patent No. 5511685 Patent Document 4: Japanese Patent No. 7014819 Summary of the Invention

[0009] The technical problem that the invention aims to solve Patent Document 1 studied the gloss of molded articles obtained from the polypropylene resin compositions disclosed therein, but did not study the appearance of the molded articles. Patent Document 2 also did not study the appearance of the molded articles.

[0010] In the molded articles obtained from the polypropylene resin compositions disclosed in Patent Documents 3 and 4, there is still room for improvement in the gloss and impact resistance of the appearance. Furthermore, in the molded articles obtained from existing propylene resin compositions in which barium sulfate and talc are added to polypropylene, there is a concern that the appearance will turn white upon impact (hereinafter also referred to as "whitening"). Moreover, Patent Documents 1 through 4 have not conducted any research on molded articles with a pearly appearance.

[0011] One embodiment of the present invention aims to provide an acrylic resin composition that yields molded articles with excellent gloss, low-temperature impact resistance, and whitening resistance, and a pearl-like appearance. Another embodiment of the present invention aims to provide molded articles and containers with excellent gloss, low-temperature impact resistance, and whitening resistance, and a pearl-like appearance.

[0012] Technical means for solving technical problems To address the aforementioned technical issues, the inventors of this invention conducted repeated and in-depth research, and discovered that the molded articles obtained from a propylene resin composition containing specific propylene polymers, specific ethylene / α-olefin copolymers, barium sulfate, talc, and nucleating agents within a specific range can achieve a pearl-like appearance, and their gloss, low-temperature impact resistance, and anti-whitening properties are superior to those of the prior art, thus completing this invention.

[0013] The technical means to solve the above-mentioned technical problems include the following methods.

[0014] <1> An acrylic resin composition, wherein, The content of propylene polymer (A) that meets the following conditions (A1) to (A5) is 40 to 85 parts by mass. The content of ethylene / α-olefin copolymer (B) that meets the following requirements (B2) and (B3) is 5 to 30 parts by weight. The content of polymer (C) is 0 to 30 parts by mass, and polymer (C) is at least one of propylene homopolymer and propylene / α-olefin random copolymer in which the content of structural units derived from α-olefin is less than 1.0% by mass relative to the total content of all structural units of the copolymer (wherein, the total content of (A), (B) and (C) above is 100 parts by mass). Compared to the total of 100 parts by mass of (A), (B), and (C) above, the content of barium sulfate is 5 to 10 parts by mass, the content of talc is 1 to 5 parts by mass, and the content of nucleating agent is 0.1 to 0.6 parts by mass. (A1): The component of the propylene polymer (A) that is insoluble in n-decane (D) insol The content of soluble components in n-decane is 88-96% by mass (D). sol The content is 4-12% by mass (of which, D) insol With D sol (The total content is set at 100% by mass). (A2): The above D sol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. sol The concentration is 1.5–2.5 dl / g; (A3): The above D sol The content of ethylene-derived structural units in D is relative to the above-mentioned D sol 100% by mass is 20-40% by mass; (A4): The above D insol The intrinsic viscosity [η] of tetrahydronaphthalene measured at 135 °C. insol The concentration was 0.8–1.3 dl / g; (A5): The melt flow rate (MFR) of propylene polymer (A) measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg is 35–170 g / 10 min; (B2): The density of the ethylene / α-olefin copolymer (B) is 886–920 kg / m³. 3 ; (B3): The melt flow rate (MFR) of ethylene / α-olefin copolymer (B), measured according to ASTM D-1238 at a test temperature of 190°C and a load of 2.16 kg, is 0.5 to 50 g / 10 minutes.

[0015] <2> The propylene resin composition as described in <1>, wherein the ethylene / α-olefin copolymer (B) also satisfies the following requirement (B1').

[0016] (B1'): The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) of the ethylene / α-olefin copolymer (B) as determined by gel permeation chromatography (GPC) is less than 3.0.

[0017] <3> The propylene resin composition as described in <1> or <2>, wherein the ethylene / α-olefin copolymer (B) described above also satisfies the following requirement (B1).

[0018] (B1): Ethylene / α-olefin copolymer (B) is an ethylene / α-olefin copolymer obtained by polymerization using a single-site catalyst.

[0019] <4> The propylene resin composition as described in any one of <1> to <3>, wherein the content of the propylene polymer (A) is 40 to 75 parts by mass, the content of the ethylene / α-olefin copolymer (B) is 5 to 30 parts by mass, and the content of the polymer (C) is 10 to 30 parts by mass (wherein the total content of (A), (B) and (C) is 100 parts by mass).

[0020] <5> The acrylic resin composition as described in any one of <1> to <4>, wherein the polymer (C) has a melt flow rate (MFR) of 0.5 to 50 g / 10 minutes as measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg.

[0021] <6> The acrylic resin composition as described in any one of <1> to <5>, wherein the melt flow rate (MFR) of the acrylic resin composition, as measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg, is 20 to 100 g / 10 minutes.

[0022] <7> A molded body formed from any one of <1> to <6> of an acrylic resin composition.

[0023] <8> The molded body as described in <7> is an injection molded body or an injection stretch blow molded body.

[0024] <9> The molded body as described in <7> is a molded body for use in entrusted equipment or household appliances.

[0025] <10> The molded body as described in <7> is a container.

[0026] Invention Effects According to one embodiment of the present invention, an acrylic resin composition capable of producing molded articles with excellent gloss, low-temperature impact resistance, and whitening resistance, and a pearly appearance, can be provided. Furthermore, according to another embodiment of the present invention, a molded article and a container with excellent gloss, low-temperature impact resistance, and whitening resistance, and a pearly appearance, can be provided. Detailed Implementation

[0027] The present invention will now be described in detail. The following description of the constituent elements is based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0028] In this specification, the numerical range indicated by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0029] In this specification, when referring to the amount of each component in the composition, if multiple substances belonging to each component are present in the composition, unless otherwise specified, the total amount of such multiple substances present in the composition is used.

[0030] In this specification, unless otherwise specified, the “~” symbol indicating a range of values ​​means that the units listed before and after it are the same.

[0031] In this specification, a combination of two or more preferred methods is a more preferred method.

[0032] In addition, unless otherwise specified in this specification, each component in the composition or each structural unit in the polymer may contain only one type, or two or more types may be used together.

[0033] The present invention will now be described in detail.

[0034] <Acrylic Resin Compositions> In the propylene resin composition of the present invention, the content of the propylene polymer (A) satisfying the following conditions (A1) to (A5) is 40 to 85 parts by mass, the content of the ethylene / α-olefin copolymer (B) satisfying the following conditions (B2) and (B3) is 5 to 30 parts by mass, and the content of polymer (C) is 0 to 30 parts by mass. This polymer (C) is at least one of a propylene homopolymer and a propylene / α-olefin random copolymer in which the content of structural units derived from α-olefins is 1.0% by mass or less relative to all structural units of the copolymer (wherein, the total content of (A), (B), and (C) is 100 parts by mass). Relative to the total 100 parts by mass of (A), (B), and (C), the content of barium sulfate is 5 to 10 parts by mass, the content of talc is 1 to 5 parts by mass, and the content of nucleating agent is 0.1 to 0.6 parts by mass.

[0035] The molded articles obtained by using acrylic resin compositions with the above-described structure have a pearl-like appearance and excellent gloss, low-temperature impact resistance, and whitening resistance. Although the reason for this is not yet certain, the mechanism can be speculated as follows.

[0036] In acrylic resin compositions, when the contents of the acrylic polymer (A) and the ethylene / α-olefin copolymer (B) are within the aforementioned range, the resulting molded articles exhibit excellent transparency and low-temperature impact resistance. Furthermore, since the acrylic resin composition contains a specific amount of nucleating agent, its rigidity and transparency are even better. By further containing specific amounts of a specific acrylic polymer and a specific ethylene / α-olefin copolymer, as well as barium sulfate, talc, and a nucleating agent in the acrylic resin composition, the resulting molded articles possess excellent transparency and gloss. The characteristic colors of the barium sulfate and talc dispersed in the resin are clearly discernible, suggesting excellent pearlescent color development.

[0037] Furthermore, since the acrylic resin composition has the above-mentioned structure, when manufacturing molded bodies such as food packaging containers, it can reduce the specific gravity and achieve excellent lightweighting compared to manufacturing molded bodies using ABS resin or polystyrene (PS) resin with a specific gravity of 1000 or more. It also has excellent rigidity, low-temperature impact resistance and transparency.

[0038] The components of the acrylic resin composition involved in this invention will be described below.

[0039] [Propylene polymer (A)] In the acrylic resin composition, the content of the acrylic polymer (A) satisfying the following conditions (A1) to (A5) is 40 to 85 parts by mass. Hereinafter, "acrylic polymer (A) satisfying conditions (A1) to (A5)" will sometimes be simply referred to as "acrylic polymer (A)".

[0040] There are no particular limitations on propylene-based polymers (A) as long as they meet the requirements (A1) to (A5). They are usually copolymers obtained by copolymerizing propylene and ethylene.

[0041] Furthermore, in the propylene polymer (A), as a comonomer component, structural units derived from α-olefins having 4 to 10 carbon atoms may be included in less than 3% by mass of all structural units constituting the propylene polymer (A) out of 100% by mass.

[0042] <<Requirements (A1)>> The component of propylene polymer (A) that is insoluble in n-decane (D) insol The content of soluble components in n-decane is 88-96% by mass (D). sol The content is 4-12% by mass, preferably the component insoluble in n-decane (D). insol The content of soluble components in n-decane is 92-96% by mass (D). sol The content is 4-8% by mass (of which, D) insol With D sol (The total is set at 100% by mass). Propylene polymers (A) are those containing components insoluble in n-decane within the above range (D). insol ) and soluble components (D sol ) polymers.

[0043] In propylene polymers (A), the component (D) that is insoluble in n-decane... insol The main components are those derived from propylene, and the components soluble in n-decane (D) sol It is mainly composed of structural units derived from propylene and ethylene.

[0044] Propylene polymers (A) typically have a polymer component consisting mainly of structural units derived from propylene and a copolymer component consisting mainly of structural units derived from propylene and ethylene.

[0045] In the above polymer composition, the content of structural units derived from propylene can be 100 mol%, and a small amount of structural units derived from ethylene and / or α-olefins with 4 to 10 carbon atoms can also be included as needed.

[0046] The copolymer components described above may contain a small amount of structural units derived from α-olefins with 4 to 10 carbon atoms, as needed.

[0047] The aforementioned propylene polymer (A) is preferably a so-called propylene-block copolymer.

[0048] The above (D) insol ) is 88% or more by mass, and (D solWhen the content of D is less than 12% by mass, the propylene polymer (A) contains sufficient D to contribute to rigidity. insol Therefore, molded bodies such as containers obtained from acrylic resin compositions also have excellent rigidity.

[0049] Furthermore, the acrylic resin composition preferably has a (D) insol ) as a continuous phase (oceanic area), and with (D sol The so-called island structure is where the dispersed phase (island portion) is located. In the above-mentioned range, the acrylic resin composition contains a component insoluble in n-decane (D...). insol ) and soluble components (D sol When ), it is easy to form (D) sol (D) is the island portion, thus suppressing reflected light and exhibiting excellent transparency. On the other hand, (D) sol ) is 4% or more by mass and (D insol When the content of ) is below 96% by mass, the propylene polymer (A) contains sufficient (D) sol Therefore, the energy absorption for impact is improved, and molded articles such as containers made from acrylic resin compositions have excellent impact resistance.

[0050] Among them, propylene polymer (A) (D) insol ) and (D sol The proportion can be determined according to the method described in the examples.

[0051] Additionally, regarding D in propylene polymer (A) insol and D sol The proportion can be adjusted to any amount by adjusting the manufacturing conditions described later.

[0052] More specifically, by making the polymerization time of [step 1] longer than that of [step 2] in the preparation method of the propylene polymer (A) described later, D can be increased. insol The proportion and decrease D sol The proportion. Furthermore, by making the polymerization time of [Process 2] longer than that of [Process 1], it is possible to reduce D. insol The proportion and increase D sol The proportion.

[0053] <<Requirements (A2)>> The above D sol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. sol The concentration is 1.5–2.5 dl / g, preferably 1.6–2.0 dl / g.

[0054] Intrinsic viscosity [η] sol When the concentration is 1.5 dl / g or higher, D solThe reduction of low molecular weight components increases the energy absorbed by impact, resulting in excellent impact resistance for molded parts such as containers made from acrylic resin compositions. Additionally, the intrinsic viscosity [η]... sol When the concentration is below 2.5 dl / g, D sol The reduction of high molecular weight components in the composition makes it easier to disperse finely in the continuous phase (components insoluble in n-decane), thus suppressing the increase in particle size. As a result, containers and other products made from propylene resin compositions exhibit excellent transparency.

[0055] Among them, the above-mentioned D of propylene polymer (A) sol The intrinsic viscosity [η] of tetrahydronaphthalene measured at 135 °C. sol It can be obtained according to the method described in the examples.

[0056] In addition, regarding D sol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. sol The adjustment of ] can be set to any amount by adjusting the manufacturing conditions described later.

[0057] More specifically, the amount of hydrogen supplied as a chain transfer agent during polymerization in step 2 of the process for producing the propylene-based polymer (A) can be adjusted. That is, by increasing the amount of hydrogen supplied relative to the amount of propylene supplied, or by increasing the amounts of propylene and ethylene supplied when supplying propylene and ethylene, the intrinsic viscosity [η] can be adjusted. sol The intrinsic viscosity [η] can be reduced when the feed rate of hydrogen is reduced relative to the feed rate of propylene or when the feed rate of propylene and ethylene is reduced. sol [Increase]

[0058] <<Requirements (A3)>> The above D sol The content of ethylene-derived structural units in the mixture is 20-40% by mass, preferably 25-35% by mass, and more preferably 28-31% by mass.

[0059] In D sol When the content of ethylene-derived structural units in D is 20% or more by mass, sol Containing ample structural units derived from ethylene, it increases the energy absorption of impacts, resulting in excellent low-temperature impact resistance for molded parts such as containers made from acrylic resin compositions. Furthermore, in D... sol When the content of ethylene-derived structural units in D is less than 35% by mass, sol The ethylene-derived structural units in the composition do not become excessive, making it easier to disperse finely in the continuous phase (components insoluble in n-decane), thus suppressing the increase in dispersed particle size. Therefore, molded articles such as containers obtained from propylene-based resin compositions exhibit excellent transparency.

[0060] Among them, the above-mentioned D of propylene polymer (A) sol The content of ethylene-derived structural units in the sample can be specified as described in the examples. 13 The C-NMR measurement method was determined.

[0061] In addition, regarding D sol The content of the ethylene-derived structural units in the mixture can be adjusted to any amount by adjusting the manufacturing conditions described later.

[0062] More specifically, in the process of producing propylene-based polymer (A), during polymerization in step 2, by increasing the ethylene feed rate relative to the propylene feed rate, the aforementioned D can be made... sol The content of ethylene-derived structural units in the D increases. Furthermore, during polymerization in [step 2], by reducing the ethylene feed rate equivalent to the propylene feed rate, the aforementioned D can be made more abundant. sol The content of ethylene-derived structural units in the material is reduced.

[0063] <<Requirements (A4)>> The above D insol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. insol The concentration ranges from 0.8 to 1.3 dl / g.

[0064] Intrinsic viscosity [η] insol When the concentration is above 0.8 dl / g, D insol The reduction of low molecular weight components in acrylic resin compositions increases the energy absorption of impacts, resulting in excellent low-temperature impact resistance for molded parts such as containers. Furthermore, the intrinsic viscosity [η] is... insol When the concentration is below 1.3 dl / g, D insol The high molecular weight components are reduced, resulting in excellent resin flowability when manufacturing molded parts such as containers, making it easy to manufacture thin-walled molded parts.

[0065] Among them, the above-mentioned D of propylene polymer (A) insol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. insol The following can be used to determine this.

[0066] The sample was obtained by calculating D using the above method. insol and D sol The precipitate (α) was obtained at the specified ratio. Approximately 25 mg of the sample was dissolved in 25 mL of tetrahydronaphthalene, and the relative viscosity η was measured in an oil bath at 135 °C. sp After diluting the tetrahydronaphthalene solution with 5 mL of tetrahydronaphthalene solvent, the relative viscosity η was measured using the same procedure. sp This dilution operation is repeated twice more to determine η when the concentration (C) is extrapolated to 0. spThe value of / C is used as the intrinsic viscosity, and this value is used as D. insol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. insol ] .

[0067] Among them, D insol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. insol The value of 】 can be set to any amount by adjusting the manufacturing conditions described later.

[0068] More specifically, the amount of hydrogen supplied as a chain transfer agent during polymerization in step 1 of the method for producing propylene-based polymers (A) can be adjusted. That is, by increasing the amount of hydrogen supplied relative to the amount of propylene supplied, or the amount of propylene and ethylene supplied when supplying propylene and ethylene, the intrinsic viscosity [η] can be adjusted. insol The intrinsic viscosity [η] can be reduced by decreasing the hydrogen supply relative to the propylene feed rate or by reducing the propylene and ethylene feed rates when supplying propylene and ethylene. insol [Increase]

[0069] <<Requirements (A5)>> According to ASTM D-1238, the melt flow rate (MFR) of the propylene polymer (A), measured at a temperature of 230°C and a load of 2.16 kg, is 35–170 g / 10 min, preferably 40–150 g / 10 min, and more preferably 50–130 g / 10 min.

[0070] When the melt flow rate (MFR) of the propylene polymer (A) is 170 g / 10 min or less, the molded articles such as containers obtained from the propylene resin composition exhibit excellent low-temperature impact resistance. Furthermore, when the melt flow rate (MFR) of the propylene polymer (A) is 35 g / 10 min or more as described above, the resin exhibits excellent flowability when using the propylene resin composition to manufacture molded articles such as containers, making it easy to manufacture thin-walled molded articles.

[0071] The melt flow rate (MFR) of the propylene polymer (A) can be adjusted to any amount by adjusting the manufacturing conditions described later.

[0072] More specifically, the amount of hydrogen supplied as a chain transfer agent in steps 1 and 2 of the process for producing the propylene-based polymer (A) can be adjusted relative to the amount of propylene and / or ethylene supplied. By increasing the amount of hydrogen supplied relative to the amount of propylene supplied or the amount of propylene and ethylene supplied when propylene and ethylene are supplied, the melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) can be increased; by decreasing the amount of hydrogen supplied relative to the amount of propylene supplied or the amount of propylene and ethylene supplied when propylene and ethylene are supplied, the melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) can be decreased.

[0073] In addition to the methods described above, the melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) can also be adjusted by melt-blending the propylene polymer obtained from polymerization in the presence of organic peroxides. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) increases by melt-blending the propylene polymer obtained from polymerization in the presence of organic peroxides. Furthermore, increasing the amount of organic peroxide added during melt-blending further increases the melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg).

[0074] When performing melt blending treatment on the propylene polymer obtained by polymerization in the presence of organic peroxide, the amount of organic peroxide used is preferably within 0.005 to 0.05 parts by mass relative to 100 parts by mass of propylene polymer.

[0075] The organic peroxides that can be used in the melt blending process in the presence of the aforementioned organic peroxides are not particularly limited, and examples include benzoyl peroxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl isopropyl carbonate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexyn-3, tert-butyl adipate, tert-butyl peroxide-3,5,5-trimethyl hexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, and 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane. Organic peroxides include 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyne-3, 1,3-bis(tert-butylperoxide isopropyl)benzene, tert-butylisopropylphenyl peroxide, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxide)cyclohexane, 2,2-bis(tert-butylperoxide)butane, p-menthane hydroperoxide, diisopropylphenyl hydroperoxide, isopropylphenyl hydroperoxide, tert-butyl hydroperoxide, p-isopropylphenyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, or 2,5-dimethyl-2,5-di(hydroperoxide)hexane. Among these, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane and 1,3-bis(tert-butylperoxide isopropyl)benzene are more preferred as organic peroxides.

[0076] The propylene polymer (A) may contain propylene of biomass origin. For example, the propylene constituting the propylene polymer (A) may be propylene of biomass origin only, or it may contain both propylene of biomass origin and propylene of fossil fuel origin.

[0077] Biomass-derived propylene refers to propylene formed from all renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, of plant or animal origin. As a carbon source, it contains 10... －12 left-right proportion 14 The carbon isotope C, measured according to ASTM D 6866, has a biomass carbon concentration (pMC) of approximately 100 (pMC).

[0078] Biomass-derived propylene can be obtained through previously known methods. From the perspective of reducing environmental impact (mainly reducing greenhouse gases), the aforementioned propylene-based polymer (A) preferably contains biomass-derived propylene.

[0079] When the polymer manufacturing conditions, such as the catalyst, polymerization process, and polymerization temperature, are the same, even if the raw material propylene includes propylene from biomass sources, except for 10 －12 ~10 －14 The ratio of left and right contains 14Aside from the carbon isotope, the molecular structure is identical to that of propylene-based polymers containing propylene from fossil fuel sources. Therefore, it is considered that propylene-based polymers containing propylene from biomass sources have no difference in properties from those containing propylene from fossil fuel sources.

[0080] The propylene polymer (A) may also contain chemically recycled propylene. The propylene constituting the propylene polymer (A) may be chemically recycled propylene alone, or it may contain chemically recycled propylene and fossil fuel-derived propylene and / or biomass-derived propylene.

[0081] Chemically recycled propylene can be obtained through previously known methods. From the perspective of reducing environmental impact (mainly reducing waste), it is preferable that the propylene-based polymer (A) contains chemically recycled propylene. When the raw material monomers of the aforementioned polymer (A) include chemically recycled monomers, since these monomers are monomers that recover polymers such as waste plastics into monomer units such as propylene through depolymerization, thermal cracking, etc., and monomers made from these monomers, the molecular structure is identical to that of propylene-based polymers composed of monomers derived from fossil fuels, provided that the polymerization catalyst, polymerization process, polymerization temperature, and other polymer manufacturing conditions are the same. Therefore, it is considered that propylene-based polymers composed of chemically recycled propylene have no change in performance compared to propylene-based polymers composed of propylene derived from fossil fuels.

[0082] [Method for manufacturing propylene polymer (A)] There are no particular limitations on the method for manufacturing the propylene polymer (A). Generally, it is preferred to copolymerize propylene and ethylene in the presence of a catalyst containing a metallocene compound or a Ziegler-Natta catalyst.

[0083] Among them, due to its wide molecular weight distribution and good formability, the preferred propylene polymer (A) is obtained by copolymerizing propylene and ethylene in the presence of a Ziegler-Natta catalyst.

[0084] <Catalysts Containing Metallocene Compounds> As catalysts containing the aforementioned metallocene compounds, examples include at least one compound selected from metallocene compounds and compounds that react with organometallic compounds, organoaluminum oxides and metallocene compounds to form ion pairs, metallocene catalysts composed of these compounds and a desired particulate support, and preferably metallocene catalysts capable of achieving stereoregular polymerization such as isotactic or syndiotactic structures.

[0085] Among the aforementioned metallocene compounds, the bridged metallocene compounds illustrated in International Publication No. 2001 / 27124 are suitable for use. In the above general formula [I], R1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 Selected from hydrogen atoms, hydrocarbon groups, and silicon-containing groups, which may be the same or different.

[0086] Examples of such hydrocarbon groups include: straight-chain hydrocarbon groups such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; branched hydrocarbon groups such as isopropyl, tert-butyl, pentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, and 1-methyl-1-isopropyl-2-methylpropyl; and cyclopentyl, cyclohexyl, and cycloheptyl. Cyclic saturated hydrocarbon groups such as cyclooctyl, norbornyl, and adamantyl; cyclic unsaturated hydrocarbon groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthrene, and anthracene; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl, and triphenylmethyl; and hydrocarbon groups containing heteroatoms such as methoxy, ethoxy, phenoxy, furanyl, N-methylamino, N,N-dimethylamino, N-phenylamino, pyranyl, and thiophene.

[0087] Examples of silicon-containing compounds include trimethylsilyl, triethylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, and triphenylsilyl.

[0088] R 5 ~R 12 Preferably, each hydrocarbon group is independently composed of 1 to 20 carbon atoms. Examples of hydrocarbon groups with 1 to 20 carbon atoms include the hydrocarbon groups described above. Furthermore, the fluorene group in general formula [I] possesses the substituent R... 5 ~R 12 It can bond with adjacent substituents to form a ring structure. Examples of fluorene groups that form such ring structures include benzo[a]fluorene, dibenzo[a]fluorene, octahydrodibenzo[a]fluorene, octamethyloctahydrobenzo[a]fluorene, and octamethyltetrahydrodicyclopentafluorene.

[0089] In the above general formula [I], the R substituted on the cyclopentadienyl ring 1 R 2 R 3 and R 4Preferably, each is a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms. Examples of hydrocarbon groups consisting of 1 to 20 carbon atoms include the aforementioned hydrocarbon groups.

[0090] More preferably R 1 and R 3 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 4 It is a hydrogen atom.

[0091] [Y] In the above general formula [I], Y, which bridges the cyclopentadienyl ring and the fluorene ring, is preferably an element of Group 14 of the periodic table, more preferably a carbon atom, a silicon atom or a germanium atom, and even more preferably a carbon atom.

[0092] R replaced on Y 13 and R 14 Preferably, the hydrocarbon groups have 1 to 20 carbon atoms. They can be the same or different from each other, and can also combine with each other to form a ring.

[0093] Examples of hydrocarbon groups having 1 to 20 carbon atoms include the hydrocarbon groups described above.

[0094] More preferably R 13 and R 14 It is an aryl group with 6 to 20 carbon atoms. Examples of aryl groups include the aforementioned cyclic unsaturated hydrocarbon groups, saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups, and cyclic unsaturated hydrocarbon groups containing heteroatoms. Furthermore, R... 13 and R 14 Each can be the same or different, and can also combine with each other to form a ring. Preferred substituents include fluoreneyl, 10-hydroanthracenylidene, and dibenzocycloheptadeceneyl.

[0095] [M and Q] In the above general formula [I], M is preferably a transition metal of Group 4 of the periodic table, and more preferably a titanium atom, a zirconium atom, or a hafnium atom.

[0096] In addition, Q is selected from the same or different combinations of halogen atoms, hydrocarbon groups, anionic ligands, or neutral ligands that can coordinate with lone pair electrons.

[0097] [j] j is an integer from 1 to 4. When j is 2 or higher, Q can be the same or different.

[0098] Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Specific examples of hydrocarbon groups can be listed as the same hydrocarbon groups mentioned above.

[0099] Specific examples of anionic ligands include: alkoxy groups such as methoxy, tert-butoxy, and phenoxy; carboxylic acid ester groups such as acetate and benzoate; and sulfonate groups such as methanesulfonate and toluenesulfonate.

[0100] Specific examples of neutral ligands capable of lone pair electron coordination include: organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0101] Q is preferably at least one halogen atom or alkyl group.

[0102] Examples of such bridging metallocene compounds include, for instance, diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconia, diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconia, diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconia, and (methyl)(phenyl)methylene( 3-tert-butyl-5-methylcyclopentadienyl)(octamethyloctahydrobenzofluorenyl)zirconium dichloride, [3-(1',1',4',4',7',7',10',10'-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentadiene)]zirconium dichloride (compounds shown in Formula [II]), compounds shown in Formula [III], etc. Among them, in the metallocene catalyst used to manufacture propylene polymers (A), compounds that can be used simultaneously with transition metal compounds of Group 4 of the periodic table shown in the above general formula [I], compounds that react with organometallic compounds, organoaluminum oxide compounds and transition metal compounds to form ion pairs, and particulate supports used as needed, can be used without restriction as disclosed in the above-mentioned publication (International Publication No. 2001 / 27124) or Japanese Patent Application Publication No. 11-315109.

[0103] (Ziegler-Natta catalyst) Propylene polymers (A) can be manufactured using highly stereoregular Ziegler-Natta catalysts. Various known catalysts can be cited as examples of such highly stereoregular Ziegler-Natta catalysts. Examples of highly stereoregular Ziegler-Natta catalysts include catalysts composed of (a) a solid titanium catalyst having magnesium atoms, titanium atoms, halogen atoms, and electron donors; (b) an organometallic compound catalyst; and (c) an organosilicon compound catalyst having at least one group selected from cyclopentyl, cyclopentenyl, cyclopentadienyl, and their derivatives.

[0104] The above-mentioned solid titanium catalyst component (a) can be prepared by contacting a magnesium compound (a-1), a titanium compound (a-2), and an electron donor (a-3).

[0105] Magnesium compounds (a-1) can be categorized as follows: magnesium compounds with reducing power, such as magnesium compounds having magnesium-carbon bonds or magnesium-hydrogen bonds; and magnesium compounds without reducing power, such as magnesium halides, alkoxy magnesium halides, allyloxy magnesium halides, alkoxy magnesium, allyloxy magnesium, and magnesium carboxylates.

[0106] When preparing solid titanium catalyst component (a), the titanium compound (a-2) is preferably a tetravalent titanium compound as shown in formula (1).

[0107] Ti(OR) g X 4－g …(1) (In formula (1), R is a hydrocarbon group, X is a halogen atom, and 0 ≤ g ≤ 4.) Specifically, examples include: titanium tetrahalides such as TiCl4, TiBr4, and TiI4; titanium trihalides such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3, and Ti(O-iso-C4H9)Br3; titanium dihalides such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(On-C4H9)2Cl2, and Ti(OC2H5)2Br2; titanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4H9)3Cl, and Ti(OC2H5)3Br; and titanium tetraalkoxy compounds such as Ti(OCH3)4, Ti(OC2H5)4, Ti(On-C4H9)4, Ti(O-iso-C4H9)4, and Ti(O-2-ethylhexyl)4.

[0108] Examples of electron donors (a-3) used in the preparation of solid titanium catalyst component (a) include alcohols, phenols, ketones, aldehydes, esters of organic or inorganic acids, organic acyl halides, ethers, amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, etc.

[0109] When the magnesium compound (a-1), titanium compound (a-2), and electron donor (a-3) described above are brought into contact, other reaction reagents such as silicon atoms, phosphorus atoms, and aluminum atoms can coexist, and a supported solid titanium catalyst component (a) can also be prepared using a support.

[0110] Solid titanium catalyst composition (a) can be prepared using all methods, including well-known methods. A few examples are given below for brief illustration.

[0111] (1) A method of reacting a solution of a magnesium compound (a-1) containing an electron donor (liquidizing agent) (a-3) with an organometallic compound to precipitate a solid, or reacting with a titanium compound (a-2) while precipitating.

[0112] (2) A method of reacting a complex consisting of a magnesium compound (a-1) and an electron donor (a-3) with an organometallic compound, followed by a reaction with a titanium compound (a-2).

[0113] (3) A method for reacting an inorganic carrier with an organomagnesia compound (a-1) with a titanium compound (a-2) and an electron donor (a-3). In this case, the contact material can be pre-contaminated with a halogen-containing compound and / or an organometallic compound.

[0114] (4) A method of obtaining a support containing magnesium compound (a-1) from a mixture of a magnesium compound (a-1) solution containing a liquefying agent and, depending on the case, a hydrocarbon solvent, an electron donor (a-3) and a support, and then contacting it with a titanium compound (a-2).

[0115] (5) A method for contacting a solution containing a magnesium compound (a-1), a titanium compound (a-2), an electron donor (a-3), and, where appropriate, a hydrocarbon solvent, with a carrier.

[0116] (6) A method for contacting a liquid organomagnesia compound (a-1) with a halogenated titanium compound (a-2). At least one electron donor (a-3) is used in this case.

[0117] (7) A method for contacting a liquid organomagnesia compound (a-1) with a halogen-containing compound, followed by contacting it with a titanium compound (a-2). In this process, at least one electron donor (a-3) is used.

[0118] (8) A method for contacting an alkoxy-containing magnesium compound (a-1) with a halogen-containing titanium compound (a-2). At least one electron donor (a-3) is used in this case.

[0119] (9) A method for contacting a complex consisting of an alkoxy magnesium compound (a-1) and an electron donor (a-3) with a titanium compound (a-2).

[0120] (10) A method of reacting a complex consisting of an alkoxy magnesium compound (a-1) and an electron donor (a-3) with an organometallic compound, and then with a titanium compound (a-2).

[0121] (11) A method for bringing magnesium compound (a-1), electron donor (a-3), and titanium compound (a-2) into contact and reacting in any order. Before the reaction, the components can be pretreated with reaction aids such as electron donor (a-3), organometallic compound, and halogenated silicon compound.

[0122] (12) A method for reacting a liquid magnesium compound (a-1) that does not have reducing ability with a liquid titanium compound (a-2) in the presence of an electron donor (a-3) to precipitate a solid magnesium-titanium complex.

[0123] (13) A method for further reacting the reaction product obtained in (12) with titanium compound (a-2).

[0124] (14) A method for further reacting the reaction product obtained in (11) or (12) above with an electron donor (a-3) and a titanium compound (a-2).

[0125] (15) A method for treating a solid obtained by pulverizing a magnesium compound (a-1), a titanium compound (a-2), and an electron donor (a-3) using any substance of halogen, halide, or aromatic hydrocarbon. This method may include steps such as pulverizing only the magnesium compound (a-1), pulverizing a coordination compound consisting of the magnesium compound (a-1) and the electron donor (a-3), or pulverizing both the magnesium compound (a-1) and the titanium compound (a-2). Furthermore, the pulverized material may be pretreated with a reaction aid and then further treated with a halogen or the like. As a reaction aid, organometallic compounds or halogenated silicon compounds may be used.

[0126] (16) A method of contacting magnesium compound (a-1) after pulverization with titanium compound (a-2). During the pulverization and / or contact of magnesium compound (a-1), an electron donor (a-3) is used with a reaction aid as required.

[0127] (17) A method for treating the compounds obtained in (11) to (16) above with halogens, halogenated compounds or aromatic hydrocarbons.

[0128] (18) A method for contacting a metal oxide, an organomagnesium (a-1) and a halogenated compound with an electron donor (a-3) and preferably with a titanium compound (a-2).

[0129] (19) A method for contacting magnesium compounds such as magnesium salts of organic acids, alkoxymagnesium, aryloxymagnesium, etc. (a-1) with titanium compounds (a-2), electron donors (a-3), and halogenated hydrocarbons as needed.

[0130] (20) A method for contacting a hydrocarbon solution containing a magnesium compound (a-1) and alkoxy titanium with an electron donor (a-3) and a titanium compound (a-2) as needed. In this case, it is preferable to have a halogenated compound such as a halogenated silicon compound coexisting.

[0131] (21) A method of reacting a liquid magnesium compound (a-1) that does not have reducing ability with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, followed by reaction with an electron donor (a-3) and a titanium compound (a-2).

[0132] As the catalyst component (b) of the above-mentioned organometallic compound, it is preferable to contain a compound selected from metals of Group I to Group III of the periodic table, specifically including organoaluminum compounds, alkyl compounds of Group I metals and aluminum, and organometallic compounds of Group II metals, etc.

[0133] Formula: R 1 m Al(OR) 2 ) n H p X q The organoaluminum compound shown is (b-1).

[0134] (where R) 1 and R 2 These are hydrocarbon groups that typically contain 1 to 15, preferably 1 to 4, carbon atoms, and they may be the same or different from each other. X represents a halogen atom, 0 < m ≤ 3, n is a number where 0 ≤ n < 3, p is a number where 0 ≤ p < 3, q ​​is a number where 0 ≤ q < 3, and m + n + p + q = 3. Formula: M 1 AlR 1 The group I metals and aluminum coordination alkyl compounds shown in Figure 4 (b-2).

[0135] (where M) 1 For Li, Na, or K, R 1 Same as above. Formula: R 1 R 2 M 2 The dialkyl compounds of Group II or Group III shown (b-3).

[0136] (where R) 1 and R 2 Same as above, M 2 (It may be Mg, Zn, or Cd.) As an example of the aforementioned organoaluminum compound (b-1), R can be listed as... 1 m Al(OR 2 ) 3－m (R) 1 and R 2 As above, m is preferably a number of 1.5 ≤ m ≤ 3) as shown in the compound, R 1 m AlX 3－m (R) 1 As above, X is a halogen, m is preferably 0 < m < 3) of the compound shown, R 1 m AlH 3－m (R) 1 As above, m is preferably 2 ≤ m < 3) of the compound shown, R 1 m Al(OR 2 ) n X q (R) 1 and R 2 As above, compounds such as those where X is a halogen, 0 < m ≤ 3, 0 ≤ n < 3, 0 ≤ q < 3, and m + n + q = 3 are shown.

[0137] As a specific example of the above-mentioned organosilicon compound catalyst component (c), organosilicon compounds such as those shown in formula (2) can be listed.

[0138] SiR 1 R 2 n (OR 3 ) 3－n …(2) (In equation (2), n is 0, 1 or 2, R) 1 R represents a group selected from cyclopentyl, cyclopentenyl, cyclopentadienyl and their derivatives. 2 and R 3 (Indicates a hydrocarbon group.) In equation (2), R is... 1Specific examples include: cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2-ethylcyclopentyl, 3-propylcyclopentyl, 3-isopropylcyclopentyl, 3-butylcyclopentyl, 3-tert-butylcyclopentyl, 2,2-dimethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, 2,2,5-trimethylcyclopentyl, 2,3,4,5-tetramethylcyclopentyl, 2,2,5,5-tetramethylcyclopentyl, 1-cyclopentylpropyl, 1-methyl-1-cyclopentylethyl, etc. cyclopentenyl or its derivatives; cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-3-cyclopentenyl, 3-methyl-3-cyclopentenyl, 2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl, 2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl-3-cyclopentenyl, 2,2,5,5-tetramethyl-3-cyclopentenyl, etc., and their derivatives; 1,3-cyclopentadienyl, 2,4-cyclopentadienyl, etc. Cyclopentadienyl groups or their derivatives thereof, including alkenyl, 1,4-cyclopentadienyl, 2-methyl-1,3-cyclopentadienyl, 2-methyl-2,4-cyclopentadienyl, 3-methyl-2,4-cyclopentadienyl, 2-ethyl-2,4-cyclopentadienyl, 2,2-dimethyl-2,4-cyclopentadienyl, 2,3-dimethyl-2,4-cyclopentadienyl, 2,5-dimethyl-2,4-cyclopentadienyl, 2,3,4,5-tetramethyl-2,4-cyclopentadienyl, etc.; and cyclopentadienyl groups as cyclopentyl, cyclopentadienyl, etc. Indene, 2-methylindene, 2-ethylindene, 2-indene, 1-methyl-2-indene, 1,3-dimethyl-2-indene, dihydroindene, 2-methyldihydroindene, 2-dihydroindene, 1,3-dimethyl-2-dihydroindene, 4,5,6,7-tetrahydroindene, 4,5,6,7-tetrahydro-2-indene, 4,5,6,7-tetrahydro-1-methyl-2-indene, 4,5,6,7-tetrahydro-1,3-dimethyl-2-indene, fluorene, etc., are derivatives of alkenyl or cyclopentadienyl groups.

[0139] Furthermore, in equation (2), R is... 2 and R 3 Specific examples of hydrocarbon groups include alkyl, cycloalkyl, aryl, aralkyl, and other hydrocarbon groups.

[0140] In R 2 Or R 3 When there are more than two, R 2 Each other or R 3 They can be the same or different, and R 2 With R 3 They can be the same or different. Furthermore, in equation (2), R... 1 With R 2 They can be bridged by alkylene groups, etc.

[0141] In the organosilicon compound shown in formula (2), R is preferred. 1 Cyclopentyl, R 2 It is an alkyl or cyclopentyl group, R 3 Organosilicon compounds that are alkyl, especially methyl or ethyl.

[0142] Specific examples of organosilicon compounds represented by formula (2) include: trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenetrimethoxysilane, fluorenyltrimethoxysilane, etc.; dicyclopentyldimethoxysilane, bis(2 2,5-Dimethylcyclopentyl)dimethoxysilane, bis(3-tert-butylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, bis(2,5-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentenyldimethoxysilane, bis(3-cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, bis-2,4-cyclopentadienyldimethoxysilane, bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane Dialkoxysilanes, including methoxysilanes, bis(1-methyl-1-cyclopentylethyl)dimethoxysilanes, cyclopentylcyclopentenyldimethoxysilanes, cyclopentylcyclopentadienyldimethoxysilanes, diindyldimethoxysilanes, bis(1,3-dimethyl-2-indyl)dimethoxysilanes, cyclopentadienylindyldimethoxysilanes, difluorenyldimethoxysilanes, cyclopentylfluorenyldimethoxysilanes, indylfluorenyldimethoxysilanes, etc.; tricyclopentylmethoxysilanes, tricyclopentenylmethoxysilanes, tricyclopentadienylmethoxysilanes... Monoalkoxysilanes, including cyclopentylethoxysilanes, tricyclopentylethoxysilanes, dicyclopentylmethylmethoxysilanes, dicyclopentylethylmethoxysilanes, dicyclopentylmethylethoxysilanes, cyclopentyldimethylmethoxysilanes, cyclopentyldiethylmethoxysilanes, cyclopentyldimethylethoxysilanes, bis(2,5-dimethylcyclopentyl)cyclopentylmethoxysilanes, dicyclopentylcyclopentenylmethoxysilanes, dicyclopentylcyclopentadienylmethoxysilanes, and diindylcyclopentylmethoxysilanes; and other ethylene-dicyclopentyldimethoxysilanes, etc.

[0143] When polymerizing propylene using a catalyst comprising the aforementioned solid titanium catalyst component (a), organometallic compound catalyst component (b), and organosilicon compound catalyst component (c), prepolymerization can be performed beforehand.

[0144] As a prepolymer, methods for polymerizing olefins can be listed under conditions in the presence of a solid titanium catalyst component (a), an organometallic compound catalyst component (b), and an organosilicon compound catalyst component (c) as needed.

[0145] Olefins used in prepolymerization can include α-olefins with 2 to 8 carbon atoms. Specifically, examples include: straight-chain olefins such as ethylene, propylene, 1-butene, and 1-octene; and 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. These can also be copolymerized.

[0146] As a condition for prepolymerization, from the viewpoint of achieving excellent polymer formation efficiency in the formal polymerization, it is preferable to produce approximately 0.1 to 1000 g, preferably 0.3 to 500 g, of polymer per 1 g of solid titanium catalyst component (a). In the prepolymerization, it is preferable to use a catalyst with a much higher concentration than that used in the formal polymerization system.

[0147] When using a catalyst like the one described above to continuously polymerize propylene in multiple stages, propylene can be copolymerized with ethylene in any stage or in all stages, provided that it does not impair the purpose of the invention.

[0148] In continuous multi-stage polymerization, methods for producing polypropylene include homopolymerization of propylene or copolymerization of propylene and ethylene in each stage. During the formal polymerization, it is preferable to use a solid titanium catalyst component (a) (or prepolymer catalyst) in an amount of about 0.0001 to 50 millimoles, preferably about 0.001 to 10 millimoles, based on the amount of titanium atoms, per 1L of polymerization volume.

[0149] The preferred organometallic compound catalyst component (b) is used in an amount of about 1 to 2000 moles of metal atoms, preferably about 2 to 500 moles, relative to 1 mole of titanium atoms in the polymerization system. The preferred organosilicon compound catalyst component (c) is used in an amount of about 0.001 to 50 moles of metal atoms, preferably about 0.01 to 20 moles, relative to 1 mole of organometallic compound catalyst component (b).

[0150] The propylene polymer (A) can be produced by any liquid-phase polymerization method, such as gas-phase polymerization, solution polymerization, or suspension polymerization, or each stage can be carried out using its own method. Furthermore, it can be produced in any manner, either continuously or semi-continuously, or by dividing the multi-stage polymerization into multiple polymerizers, for example, 2 to 10 polymerizers. Industrially, continuous polymerization is preferred, in which case it is preferable to divide the polymerization from the second stage onwards into two or more polymerizers, thereby suppressing gel formation.

[0151] Inert hydrocarbons can be used as polymerization media, or liquid propylene can be used. Furthermore, the polymerization conditions for each stage can be appropriately selected within the polymerization temperature range of approximately -50 to +200°C, preferably approximately 20 to 100°C. Additionally, the polymerization pressure can be appropriately selected within the range of atmospheric pressure to 10 MPa (gauge pressure), preferably approximately 0.2 to 5 MPa (gauge pressure).

[0152] When manufacturing propylene polymer (A), it is preferable to use a reaction apparatus in which two or more polymerizers are connected in series to continuously perform the following two steps ([Step 1] and [Step 2]). A polymerization apparatus consisting of two or more reaction devices connected in series can be used to perform [Step 1] in each polymerization device, and a polymerization apparatus consisting of two or more reaction devices connected in series can be used to perform [Step 2] in each polymerization device.

[0153] In addition to the above methods, [Step 1] and [Step 2] can be performed separately to melt-blend the polymers obtained by each process using a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc., to produce a propylene polymer (A).

[0154] The following describes a method for manufacturing a propylene polymer (A) by continuously performing [Step 1] and [Step 2].

[0155] [Process 1] [Process 1] is a process in which propylene is (co-polymerized) with ethylene as needed at a polymerization temperature of 0 to 100°C and a polymerization pressure of atmospheric pressure to 5 MPa gauge pressure.

[0156] In [Step 1], by reducing the amount of ethylene supplied relative to propylene, or by not supplying ethylene at all, the propylene-based (co)polymer obtained in [Step 1] becomes D. insol The main component. Alternatively, a chain transfer agent, such as hydrogen, may be introduced as needed, which can also adjust the intrinsic viscosity [η] of the polymer generated in [Step 1].

[0157] [Process 2] [Step 2] is a process 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.

[0158] In [Step 2], by increasing the feed ratio of ethylene to propylene to a higher ratio than in [Step 1], the propylene-ethylene copolymer rubber produced in [Step 2] becomes D. sol The main component. Alternatively, a chain transfer agent, such as hydrogen, may be introduced as needed to adjust the intrinsic viscosity [η] of the polymer generated in [Step 2].

[0159] The propylene polymer (A) can be obtained by continuously performing the above-described steps [Step 1] and [Step 2], wherein the requirement (A1), namely the above-described D, is... insol With D sol The content ratio can be adjusted by adjusting the polymerization time of [process 1] and [process 2] above.

[0160] That is, by making the polymerization time of [process 1] longer than that of [process 2], D can be increased. insol The proportion, reducing D sol The proportion. Furthermore, by making the polymerization time of [step 2] longer than that of [step 1], it is possible to reduce D. insol The proportion of D increases sol The proportion.

[0161] Involving D sol The requirement (A2) can be adjusted by adjusting the amount of hydrogen supplied as a chain transfer agent during [Step 2]. That is, by increasing the amount of hydrogen supplied relative to the amount of propylene supplied, or by increasing the amount of propylene and ethylene supplied when supplying propylene and ethylene, the intrinsic viscosity [η] can be adjusted. sol [Reduce]; by reducing the amount of hydrogen supplied relative to the propylene feed rate or the propylene and ethylene feed rates when supplying propylene and ethylene, it is possible to reduce D sol intrinsic viscosity [η] sol [Increase]

[0162] Involving D sol The requirement (A3) can be adjusted by adjusting the propylene and ethylene feed rates during [Step 2]. That is, by increasing the ethylene feed rate relative to the propylene feed rate, the aforementioned D... sol The weight of the ethylene-derived structural units in the D increases. Furthermore, by reducing the ethylene feed rate relative to the propylene feed rate, the aforementioned D... sol The weight of the structural units derived from ethylene is reduced.

[0163] Involving D insolThe requirement (A4) can be adjusted by adjusting the amount of hydrogen supplied as a chain transfer agent during [Step 1]. That is, by increasing the amount of hydrogen supplied relative to the amount of propylene supplied, or by increasing the amount of propylene and ethylene supplied when supplying propylene and ethylene, the intrinsic viscosity [η] can be adjusted. insol The intrinsic viscosity [η] can be reduced by decreasing the amount of hydrogen supplied relative to the propylene feed rate or by reducing the amount of propylene and ethylene supplied when supplying propylene and ethylene. insol [Increase]

[0164] Requirement (A5) can be adjusted by adjusting the amount of hydrogen, which acts as a chain transfer agent, relative to the amount of propylene supplied during [Step 1] or [Step 2], or relative to the amount of propylene and ethylene supplied during the supply of propylene and ethylene. Increasing the amount of hydrogen supplied relative to the amount of propylene supplied, or relative to the amount of propylene and ethylene supplied during the supply of propylene and ethylene, can increase the melt flow rate (MFR); decreasing the amount of hydrogen supplied relative to the amount of propylene supplied, or relative to the amount of propylene and ethylene supplied during the supply of propylene and ethylene, can decrease the MFR.

[0165] In addition to the methods described above, the melt flow rate of the propylene polymer (A) obtained by polymerization can be adjusted to the range of 35 to 170 g / 10 minutes by melt-blending the polymer under conditions of organic peroxides. This was done according to ASTM D-1238, at a test temperature of 230°C and a load of 2.16 kg.

[0166] By melt-blending the propylene polymer (A) obtained from polymerization under conditions of organic peroxide, the melt flow rate (MFR) of the propylene polymer (A) (ASTM D-1238, test temperature 230°C, load 2.16 kg) increased. By increasing the amount of organic peroxide added during melt-blending under conditions of organic peroxide, the melt flow rate (MFR) of the propylene polymer (A) (ASTM D-1238, test temperature 230°C, load 2.16 kg) further increased. When melt-blending the propylene polymer (A) obtained from polymerization under conditions of organic peroxide, it is desirable to use 0.005 to 0.05 parts by mass of organic peroxide per 100 parts by mass of the propylene polymer. Furthermore, the melt-blending treatment under conditions of organic peroxide described above can also be performed after the following post-processing steps.

[0167] The organic peroxides that can be used in the melt blending process under the aforementioned organic peroxide conditions are not particularly limited, and examples include benzoyl peroxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl isopropyl carbonate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexyn-3, tert-butyl dipyridyl peroxide, tert-butyl peroxide-3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, and 2,5-dimethyl-2,5-di(tert-butyl peroxide). Organic peroxides include hexane (peroxide), 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyne-3, 1,3-bis(tert-butylperoxide isopropyl)benzene, tert-butylisopropylphenyl peroxide, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxide)cyclohexane, 2,2-bis(tert-butylperoxide)butane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, p-isopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, or 2,5-dimethyl-2,5-di(hydroperoxide)hexane. Among these, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane and 1,3-bis(tert-butylperoxide isopropyl)benzene are more preferred.

[0168] After polymerization, known post-processing steps such as catalyst deactivation, catalyst residue removal, and drying are performed as needed, thereby obtaining a propylene polymer (A) in powder form.

[0169] [Ethylene / α-olefin copolymer (B)] In the acrylic resin composition, the content of the ethylene / α-olefin copolymer (B) satisfying the following requirements (B2) and (B3) is 5 to 30 parts by mass (wherein, the total content of (A), (B) and (C) above is 100 parts by mass). The term "ethylene / α-olefin copolymer (B) satisfying requirements (B2) and (B3)" is sometimes also written as "ethylene / α-olefin copolymer (B)".

[0170] The ethylene / α-olefin copolymer (B) may contain one or more types.

[0171] There are no particular limitations on the ethylene / α-olefin copolymer (B) as long as requirements (B2) and (B3) are met. From the perspective of good low-temperature impact resistance and transparency, the copolymer obtained by copolymerizing ethylene and α-olefins with 3 to 20 carbon atoms is preferred as the ethylene / α-olefin copolymer (B).

[0172] Examples of α-olefins with 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, α-olefins with 4 to 10 carbon atoms are preferred from the perspectives of transparency, low-temperature impact resistance, rigidity, and economy.

[0173] <<Requirement (B2)>> The density of ethylene / α-olefin copolymer (B) is 886–920 kg / m³. 3 .

[0174] The density of the ethylene / α-olefin copolymer (B) is 886 kg / m³. 3 At the above levels, the number of branches decreases, resulting in crystallinity, and the refractive index difference with the propylene polymer (A) also decreases. Therefore, the molded articles obtained from the propylene resin composition exhibit excellent rigidity and transparency. Furthermore, the density of the ethylene / α-olefin copolymer (B) is 920 kg / m³. 3 When crystallinity decreases, the refractive index difference with the propylene polymer (A) also decreases, resulting in excellent transparency of molded articles and the like obtained from the propylene resin composition.

[0175] Furthermore, the density of the ethylene / α-olefin copolymer (B) can be adjusted to any amount by adjusting the manufacturing conditions described later.

[0176] More specifically, the density can be adjusted by changing the ratio of ethylene to α-olefin feed amounts during the polymerization of the ethylene / α-olefin copolymer (B), as described later. Specifically, increasing the α-olefin feed amount relative to the ethylene feed amount reduces the density, while decreasing the α-olefin feed amount relative to the ethylene feed amount increases the density.

[0177] The density of the ethylene / α-olefin copolymer (B) is determined as follows: the stock obtained when measuring the melt flow rate of the ethylene / α-olefin copolymer (B) (ASTM D-1238, measurement temperature 190℃, load 2.16kg) is heat-treated at 120℃ for 1 hour and then slowly cooled to room temperature for 1 hour. The resulting material is used as a sample and the density is measured using the density gradient tube method. The measured value is determined as the density of the ethylene / α-olefin copolymer (B).

[0178] <<Requirements (B3)>> According to ASTM D-1238, the melt flow rate (MFR) of ethylene / α-olefin copolymer (B), measured at a test temperature of 190°C and a load of 2.16 kg, is 0.5 to 50 g / 10 min, preferably 2 to 5 g / 10 min.

[0179] When the melt flow rate (MFR) (ASTM D-1238, test temperature 190°C, load 2.16 kg) of ethylene / α-olefin copolymer (B) is 0.5 g / 10 min, the molecular weight decreases, resulting in excellent resin flowability when manufacturing molded parts such as containers, thus facilitating the production of thin-walled molded parts. When the melt flow rate (MFR) (ASTM D-1238, test temperature 190°C, load 2.16 kg) of ethylene / α-olefin copolymer (B) is below 50 g / 10 min, the molecular weight increases, leading to improved impact energy absorption. Therefore, molded parts obtained from acrylic resin compositions exhibit excellent impact resistance.

[0180] The melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) (ASTM D-1238, test temperature 190°C, load 2.16 kg) can be adjusted to any amount by adjusting the manufacturing conditions described later.

[0181] More specifically, the hydrogen supply can be adjusted in the polymerization of ethylene / α-olefin copolymer (B) by adjusting the amount of hydrogen supplied relative to the amount of ethylene and / or α-olefin fed during polymerization. Increasing the hydrogen supply relative to the amount of ethylene gas fed during polymerization, or relative to the amount of ethylene and α-olefin fed during polymerization, increases the melt flow rate (MFR) (ASTM D-1238, test temperature 190°C, load 2.16 kg). Conversely, decreasing the hydrogen supply relative to the amount of ethylene gas fed, or relative to the amount of ethylene and α-olefin fed during polymerization, decreases the melt flow rate (MFR) (ASTM D-1238, test temperature 190°C, load 2.16 kg).

[0182] The ethylene / α-olefin copolymer (B) preferably also satisfies the following requirement (B1').

[0183] <<Requirements (B1')>> The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the ethylene / α-olefin copolymer (B), as measured by gel permeation chromatography (GPC), is 3.0 or less, preferably 1.5 to 3.0, more preferably 1.8 to 3.0, and even more preferably 2.0 to 3.0.

[0184] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) can be determined by the measurement methods described in the examples below.

[0185] The ethylene / α-olefin copolymer (B) preferably also satisfies the following requirement (B1).

[0186] <<Requirements (B1)>> Ethylene / α-olefin copolymer (B) is an ethylene / α-olefin copolymer obtained by polymerization using a single-site catalyst.

[0187] Examples of unit-site catalysts include (a) transition metal compounds described later, (b) organoaluminum oxides, (c) particulate supports, and (d) organoaluminum compounds as needed, unit-site olefin polymerization catalysts.

[0188] When the ethylene / α-olefin copolymer (B) is an ethylene / α-olefin copolymer obtained by polymerization using a single-point catalyst, the compositional distribution is more uniform than that of existing ethylene / α-olefin copolymers obtained by polymerization using so-called Ziegler-Natta catalysts, thus enabling the production of propylene resin compositions with excellent transparency.

[0189] Furthermore, when the ethylene / α-olefin copolymer (B) is an ethylene / α-olefin copolymer obtained by polymerization using a single-point catalyst, the molecular weight distribution is narrower than that of the ethylene / α-olefin copolymer obtained by polymerization using a Ziegler-Natta catalyst, resulting in a reduction in low molecular weight components that are the main factor contributing to the decrease in low-temperature impact resistance.

[0190] In summary, the propylene resin composition containing ethylene / α-olefin copolymer obtained by polymerization using a single-point catalyst produces molded articles with excellent transparency and excellent low-temperature impact resistance.

[0191] Examples of catalysts that can be considered as single-site catalysts include catalysts containing geometrically structured complexes (so-called geometrically structured catalysts (also known as CGC (constrained geometry catalyst) catalysts)) or catalysts containing metallocene compounds. Among these, catalysts containing metallocene compounds are preferred as single-site catalysts, especially from the perspective of good low-temperature impact resistance.

[0192] In the ethylene / α-olefin copolymer (B), the ethylene and α-olefin constituting the copolymer (B) may include biomass-derived monomers. For example, the monomers constituting the copolymer (B) may be solely biomass-derived monomers, or they may include both biomass-derived monomers and fossil fuel-derived monomers.

[0193] For example, the monomers constituting copolymer (B) may be solely biomass-derived monomers, or they may include both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers refer to monomers formed from all renewable natural raw materials and their residues, including plant-based or animal-based sources such as fungi, yeasts, algae, and bacteria. As for carbon, they contain 10... －12 left-right proportion 14 The carbon isotope concentration (pMC) of the biomass, measured according to ASTM D 6866, is approximately 100 pMC. Biomass-derived monomers can be obtained using previously known methods. From the perspective of reducing environmental impact (primarily reducing greenhouse gases), ethylene / α-olefin copolymers (B) containing biomass-derived monomers are preferred. When polymer manufacturing conditions such as polymerization catalysts, polymerization processes, and polymerization temperatures are identical, even if the raw material monomers contain biomass-derived monomers, except for those with a pMC of 10... －12 ~10 －14 The ratio of left and right contains 14 Apart from the carbon isotope, the molecular structure is also identical to that of ethylene / α-olefin copolymers composed of monomers derived from fossil fuels. Therefore, it is considered that ethylene / α-olefin copolymers composed of monomers derived from biomass have no change in performance compared to ethylene / α-olefin copolymers composed of monomers derived from fossil fuels.

[0194] The ethylene / α-olefin copolymer (B) may also contain chemically recycled monomers (ethylene, α-olefins). For example, the monomers constituting the copolymer (B) may be solely chemically recycled monomers, or they may include chemically recycled monomers, fossil fuel-derived monomers, and / or biomass-derived monomers. Chemically recycled monomers can be obtained by methods known in the past. From the perspective of reducing environmental impact (mainly reducing waste), it is preferable that the ethylene / α-olefin copolymer (B) contains chemically recycled monomers. Even if the raw material monomers contain chemically recycled monomers, since chemically recycled monomers are monomers that recover polymers such as waste plastics into monomer units such as ethylene through depolymerization, thermal cracking, etc., and monomers made from these monomers, as long as the polymer manufacturing conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, the molecular structure is the same as that of the ethylene / α-olefin copolymer composed of fossil fuel-derived monomers. Therefore, it is considered that the ethylene / α-olefin copolymer composed of chemically recycled monomers has no change in performance compared to the ethylene / α-olefin copolymer composed of fossil fuel-derived monomers.

[0195] <Method for manufacturing ethylene / α-olefin copolymer (B)> The following describes the olefin polymerization catalysts used in the production of ethylene / α-olefin copolymer (B) and the components of each catalyst.

[0196] (a) The transition metal compound (hereinafter sometimes referred to as “component (a)”) is preferably a transition metal compound represented by the following formula (I).

[0197] MLx …(I) In formula (I), M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

[0198] x is the valence of the transition metal atom represented by M, and indicates the number of L ligands coordinated with the transition metal atom. L are ligands coordinated with the transition metal atom M, of which at least two ligands L are cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, or substituted cyclopentadienyl with at least one substituent selected from hydrocarbon groups having 3 to 10 carbon atoms. Ligands L other than (substituted)cyclopentadienyl are hydrocarbon groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups, or hydrogen atoms having 1 to 12 carbon atoms.

[0199] The substituted cyclopentadienyl group can have two or more substituents, which can be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent must be a hydrocarbon group with 3 to 10 carbon atoms, and the other substituents can be methyl, ethyl, or a hydrocarbon group with 3 to 10 carbon atoms. Furthermore, the substituted cyclopentadienyl group coordinated to M can be the same or different.

[0200] Examples of hydrocarbon groups with 3 to 10 carbon atoms include alkyl, cycloalkyl, aryl, and aralkyl groups. More specifically, examples include alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl.

[0201] Alkyl groups are preferred among these, especially n-propyl and n-butyl. As a (substituted) cyclopentadienyl group coordinated with a transition metal, a substituted cyclopentadienyl group is preferred, a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms is more preferred, a disubstituted cyclopentadienyl group is even more preferred, and a 1,3-substituted cyclopentadienyl group is particularly preferred.

[0202] In addition, in the above formula (I), the ligand L other than the (substituted) cyclopentadienyl group coordinated with the transition metal atom M is a hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom with 1 to 12 carbon atoms.

[0203] Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl, cycloalkyl, aryl, and aralkyl groups. More specifically, examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl.

[0204] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, and octoxy.

[0205] Examples of aryloxy groups include phenoxy groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0206] Examples of trialkylsilyl compounds include trimethylsilyl, triethylsilyl, and triphenylsilyl.

[0207] Examples of transition metal compounds represented by such general formula (I) include bis(cyclopentadienyl)zirconia dichloride, bis(methylcyclopentadienyl)zirconia dichloride, bis(ethylcyclopentadienyl)zirconia dichloride, bis(n-propylcyclopentadienyl)zirconia dichloride, bis(n-butylcyclopentadienyl)zirconia dichloride, bis(n-hexylcyclopentadienyl)zirconia dichloride, bis(methyln-propylcyclopentadienyl)zirconia dichloride, bis(methyln-butylcyclopentadienyl)zirconia dichloride, bis(dimethyln-butylcyclopentadienyl)zirconia dichloride, and bis(n-butylcyclopentadienyl)zirconia dichloride. Zirconium dibromide (dienyl), bis(n-butylcyclopentadienyl)methoxyzirconium chloride, bis(n-butylcyclopentadienyl)ethoxyzirconium chloride, bis(n-butylcyclopentadienyl)butoxyzirconium chloride, bis(n-butylcyclopentadienyl)ethoxyzirconium, bis(n-butylcyclopentadienyl)methylzirconium chloride, bis(n-butylcyclopentadienyl)dimethylzirconium, bis(n-butylcyclopentadienyl)benzylzirconium chloride, bis(n-butylcyclopentadienyl)dibenzylzirconium, bis(n-butylcyclopentadienyl)phenylzirconium chloride, bis(n-butylcyclopentadienyl)zirconium hydrochloride, etc.

[0208] In the examples above, the disubstituted forms of the cyclopentadienyl ring include 1,2- and 1,3-substituted forms, and the trisubstituted forms include 1,2,3- and 1,2,4-substituted forms. In this invention, transition metal compounds in which zirconium metal in the above-described zirconium compounds is replaced with titanium or hafnium metal can be used.

[0209] Among these transition metal compounds represented by general formula (I), bis(n-propylcyclopentadienyl)zirconia, bis(n-butylcyclopentadienyl)zirconia, bis(1-methyl-3-n-propylcyclopentadienyl)zirconia, and bis(1-methyl-3-n-butylcyclopentadienyl)zirconia are particularly preferred.

[0210] The organoaluminum oxide (b) (hereinafter sometimes referred to as "component (b)") may be a known aluminum oxide that is soluble in benzene, or it may be an organoaluminum oxide that is insoluble in benzene as disclosed in Japanese Patent Application Publication No. 2-276807.

[0211] Existing known aluminum oxanes can be manufactured, for example, by contacting the organoaluminum compound described below with water such as adsorbed water, water of crystallization, ice, or water vapor, or by reacting the organoaluminum compound described below with organotin oxides.

[0212] The particulate support (c) can be an inorganic or organic compound, and can be a particulate or microparticle solid with an average particle size of 10–300 μm, preferably 20–200 μm. Among them, porous oxides are preferred as inorganic supports, specifically including SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof, such as SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc.

[0213] Among these, materials with at least one component selected from SiO2 and Al2O3 as the main component are preferred.

[0214] Furthermore, the aforementioned inorganic oxides are also permitted to contain small amounts of carbonates, sulfates, nitrates, and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0215] The properties of such particulate carriers (c) vary depending on the type and preparation method, and the specific surface area of ​​the particulate carriers ranges from 50 to 1000 m². 2 / g, preferably 100-700m 2 / g, with a preferred pore volume of 0.3–2.5 cm³. 3 / g. This particulate carrier can be used after firing at 100–1000°C, preferably 150–700°C, as needed.

[0216] In addition, particulate or microparticle solids of organic compounds with an average particle size of 10 to 300 μm can be cited as examples of particulate carriers. Examples of these organic compounds include (co)polymers with α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or polymers or copolymers with vinylcyclohexane and styrene as the main components.

[0217] The olefin polymerization catalyst used to manufacture the ethylene / α-olefin copolymer (B) can be formed from the particulate support of the above components (a), (b) and (c), but may also use organoaluminum compounds (d) as needed.

[0218] As an organoaluminum compound (hereinafter sometimes referred to as "component (d)") used as required, organoaluminum compounds of the following general formula (III) can be exemplified, for example.

[0219] R 1 nAlX3-n …(III) (where R) 1 (This represents a hydrocarbon group with 1 to 12 carbon atoms, where X represents a halogen or hydrogen atom, and n is 1 to 3.) In the above general formula (III), R 1 It is a hydrocarbon group with 1 to 12 carbon atoms, such as alkyl, cycloalkyl or aryl, specifically methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, etc.

[0220] Examples of such organoaluminum compounds include: trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminum such as isopreneylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

[0221] Alternatively, as organoaluminum compounds (d), compounds represented by the following general formula (IV) can also be used.

[0222] R 1 n AlY3-n …(IV) (In equation (IV), R) 1 R represents the expression in general formula (III) above. 1 The same hydrocarbon group, Y represents -OR 2 base, -OSiR 33 base, -OAlR 42 base, -NR 52 basal, -SiR 63 base or -N(R) 7 AlR 82 Basis, n is 1 to 2, R 2 R 3 R4 and R 8 For example, methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc., R 5 For hydrogen atoms, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., R 6 and R 7 (These include methyl, ethyl, etc.) Of such organoaluminum compounds, R is preferred. 1 nAl(OAlR 42 ) 3－n The compounds shown include, for example, Et2AlOAlEt2, (iso-Bu)2AlOAl(iso-Bu)2, etc.

[0223] Of the organoaluminum compounds represented by general formulas (III) and (IV) above, general formula R is preferred. 13 The compound represented by Al is particularly preferred by R. 1 It is an isoalkyl compound.

[0224] In the manufacture of ethylene / α-olefin copolymer (B), a catalyst prepared by contacting the above-mentioned components (a), components (b), particulate support (c), and components (d) as needed is used.

[0225] The contact of the above components can be carried out in a non-reactive hydrocarbon solvent. The non-reactive hydrocarbon media used to prepare the catalyst can be specifically listed as aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as vinyl chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0226] The catalyst used to produce the ethylene / α-olefin copolymer (B) can also be a prepolymer catalyst capable of prepolymerizing the olefin in the presence of the above-mentioned components (a), (b), particulate support (c), and, if necessary, component (d). Prepolymerization can be carried out by introducing the olefin into an inert hydrocarbon solvent in the presence of the above-mentioned components (a), (b), particulate support (c), and, if necessary, component (d).

[0227] Examples of olefins used in prepolymerization include ethylene and α-olefins with 3 to 20 carbon atoms, as described above. Among these, ethylene, or a combination of ethylene and α-olefins with 3 to 20 carbon atoms, is particularly preferred as the olefin used in prepolymerization.

[0228] Prepolymerization can be carried out in any manner, either batch or continuous, and under any conditions, including reduced pressure, normal pressure, or pressurized pressure. During prepolymerization, it is preferable to coexist with hydrogen gas to produce a prepolymer with an intrinsic viscosity [η] of 0.2–7 dl / g, preferably 0.5–5 dl / g, as measured at least in decahydronaphthalene at 135°C.

[0229] The ethylene / α-olefin copolymer (B) is preferably obtained by gas-phase polymerization of ethylene or gas-phase copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of the aforementioned olefin polymerization catalyst or prepolymerization catalyst. Furthermore, a chain transfer agent, such as hydrogen, can be introduced as needed to adjust the molecular weight of the resulting polymer, thereby allowing adjustment of the melt flow rate (MFR) (ASTM D-1238, test temperature 190°C, load 2.16 kg).

[0230] During polymerization, the amount of the aforementioned olefin polymerization catalyst or prepolymerization catalyst is preferably 10% based on the transition metal atom concentration in the polymerization reaction system. －8 ~10 －3 gram atoms per liter, preferably 10 －7 ~10 －4 gram atoms per liter.

[0231] Furthermore, during polymerization, the same organoaluminum oxide compound and / or organoaluminum compound (d) as component (b) may be added. In this case, the atomic ratio (Al / M) of aluminum atoms (Al) from the organoaluminum oxide compound and organoaluminum compound to transition metal atoms (M) from the transition metal compound (a) is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

[0232] The polymerization temperature is typically in the range of 0–120°C, preferably 20–100°C. The polymerization pressure is typically from atmospheric pressure to 100 kg / cm². 2 The preferred value is 2-50 kg / cm². 2 Under the given pressurized conditions, polymerization can be carried out in any manner, including batch, semi-continuous, and continuous processes.

[0233] Furthermore, it can also separate polymerization into two or more stages with different reaction conditions.

[0234] The ethylene / α-olefin copolymer (B) is manufactured through the above-described process. The requirement (B2) for the ethylene / α-olefin copolymer (B) can be adjusted by changing the ratio of the ethylene to α-olefin feed amounts in the polymerization process. Increasing the α-olefin feed amount relative to the ethylene feed amount results in a lower density, while decreasing the α-olefin feed amount relative to the ethylene feed amount results in a higher density.

[0235] Regarding requirement (B3) for the ethylene / α-olefin copolymer (B), it can be adjusted by changing the feed rate of ethylene in the above polymerization process, or by the ratio of the feed rate of ethylene and α-olefin to the feed rate of hydrogen as a chain transfer agent. By increasing the feed rate of hydrogen relative to the feed rate of ethylene or the feed rate of ethylene and α-olefin, the melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) (ASTM D-1238, test temperature 190°C, load 2.16 kg) can be increased. Conversely, by decreasing the feed rate of hydrogen relative to the feed rate of ethylene or the feed rate of ethylene and α-olefin, the melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) (ASTM D-1238, test temperature 190°C, load 2.16 kg) can be decreased.

[0236] [Polymer (C)] In the propylene resin composition, polymer (C) is at least one of propylene homopolymer and propylene / α-olefin random copolymer (hereinafter sometimes referred to as "propylene / α-olefin random copolymer") in which the content of structural units derived from α-olefin is less than 1.0% by mass relative to all structural units of the copolymer (hereinafter sometimes simply referred to as "polymer (C)"). The content of polymer (C) is 0 to 30 parts by mass, preferably 10 to 25 parts by mass, more preferably 15 to 20 parts by mass (wherein the total content of (A), (B) and (C) is 100 parts by mass).

[0237] In the case of both propylene homopolymer and propylene / α-olefin random copolymer, the above content refers to the total content of propylene homopolymer and propylene / α-olefin random copolymer.

[0238] The polymer (C) may contain one or more types.

[0239] Examples of α-olefins constituting propylene / α-olefin random copolymers include ethylene and α-olefins with 4 to 20 carbon atoms. Among these, ethylene and α-olefins with 4 to 10 carbon atoms are preferred.

[0240] Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Among these, ethylene and 1-butene are preferred as the aforementioned α-olefins, with ethylene being particularly preferred.

[0241] The content of α-olefin-derived structural units in the propylene / α-olefin random copolymer is 1.0% by mass or less, preferably 0.8% by mass or less, and more preferably 0.5% by mass or less, relative to the total number of structural units in the copolymer. There is no particular limitation on the lower limit of the content of α-olefin-derived structural units, but it is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more.

[0242] In propylene / α-olefin random copolymers, one type of α-olefin can be used alone, or two or more types can be used together.

[0243] The melt flow rate (MFR) of the polymer (C) measured according to ASTM D-1238 at a temperature of 230°C and a load of 2.16 kg is preferably 0.5 to 50 g / 10 min, more preferably 2 to 20 g / 10 min, and even more preferably 10 to 20 g / 10 min. When the MFR is within the above range, the acrylic resin composition can be easily injection molded, and molded articles with excellent rigidity and heat resistance can be obtained.

[0244] When a composition contains two or more polymers (C), the MFR of the polymer (C) is determined by mixing and melting the polymers (C) separately and measuring the MFR of the resulting mixture.

[0245] The melting point (Tm) of the polymer (C) is preferably in the range of 155 to 170°C, more preferably in the range of 158 to 167°C.

[0246] When the melting point (Tm) of the above polymer is in the range of 155 to 170°C, the resulting molded articles have excellent rigidity and heat resistance.

[0247] When the composition contains two or more polymers (C), it is preferable that the melting points (Tm) of all polymers (C) are in the range of 155 to 170°C.

[0248] The melting point mentioned above was determined using a differential scanning calorimetry (DSC) instrument. The temperature at the peak of the melting peak was observed after the temperature was held at 200°C for 10 minutes, cooled to -20°C at a rate of 10°C / min, held at -20°C for 1 minute, and then heated back to 200°C at a rate of 10°C / min.

[0249] The polymer (C) may contain propylene from biomass sources. For example, the propylene constituting the above-mentioned propylene homopolymer or the above-mentioned propylene / α-olefin random copolymer may be propylene from biomass sources only, or it may contain both propylene from biomass sources and propylene from fossil fuel sources.

[0250] Furthermore, polymer (C) may contain propylene from a chemically recycled source.

[0251] The meanings of the above-mentioned biomass-derived propylene and chemically regenerated propylene are the same as those of the above-mentioned propylene-based polymers (A) in terms of biomass-derived propylene and chemically regenerated propylene.

[0252] As a method for manufacturing polymer (C), catalysts for olefin polymerization, such as Ziegler-Natta catalysts or metallocene catalysts, can be used. As an example of a Ziegler-Natta catalyst, a solid titanium catalyst component consisting of active magnesium compounds, titanium compounds, halogen compounds, and internal electron donors can be supported on an organic or inorganic support, and an organometallic compound component of metals from Groups I to III of the periodic table can be added thereto, along with an external electron donor catalyst system.

[0253] Polymer (C) can be synthesized or commercially available products can be used. Examples of commercially available products include J106G (trade name) produced by Praman Polymers Co., Ltd., a propylene homopolymer.

[0254] Barium sulfate Barium sulfate is an inorganic compound represented by the chemical formula BaSO4. There are no particular limitations on the type of barium sulfate used; examples include barite powder obtained by crushing barite and precipitating barium sulfate obtained through the metathesis of barium sulfide and sodium sulfate. From the perspective of fine particle size and the tendency to exhibit a pearly hue, precipitating barium sulfate is preferred.

[0255] The content of barium sulfate is 5 to 10 parts by mass, preferably 6 to 8 parts by mass, relative to a total of 100 parts by mass of the above-mentioned propylene polymer (A), the above-mentioned ethylene / α-olefin copolymer (B) and the above-mentioned polymer (C).

[0256] When the barium sulfate content is within the above range, the brightness (i.e., pearly luster) of the pearl color is superior. Furthermore, the density of the acrylic resin composition and the resulting molded article is less likely to become excessive.

[0257] Barium sulfate can be a single substance or a combination of two or more substances.

[0258] Barium sulfate can be synthesized or is commercially available. Examples of commercially available products include, for instance, precipitating barium sulfate (grade 300) produced by Sakai Chemical Industry Co., Ltd.

[0259] 〔talc〕 Talc is a hydrated magnesium silicate with the chemical formula Mg3Si4O 10 (OH)2) represents an inorganic substance. There are no particular limitations on what can be used as talc; for example, white talc can be listed.

[0260] In addition, the average particle size of talc is preferably 1.0 to 5.0 μm, more preferably 1.5 to 4.5 μm, and even more preferably 2.0 to 4.0 μm.

[0261] The aforementioned average particle size refers to the particle size distribution on a volume basis determined by laser diffraction, where the cumulative particle size distribution from the smallest particle size side reaches 50% (i.e., the cumulative value in the particle size distribution). Specifically, it is determined using a laser diffraction particle size distribution measuring device (product name: "SALD-2000", manufactured by Shimadzu Corporation) according to the measurement method based on JIS R1629.

[0262] The talc content is 1 to 5 parts by mass, preferably 2 to 3 parts by mass, relative to 100 parts by mass of the above-mentioned propylene polymer (A), the above-mentioned ethylene / α-olefin copolymer (B) and the above-mentioned polymer (C).

[0263] When the talc content is within the above range, it is easy to obtain a molded article with a pearlescent color, and the density of the acrylic resin composition and the resulting molded article is not likely to become too high.

[0264] Talc can be a single type or a combination of two or more types.

[0265] Talc can be synthesized or is commercially available. As a commercially available product, examples include HI-FILLER 5000PJ manufactured by Matsumura Sangyo Co., Ltd.

[0266] [Nucleating agent] As a nucleating agent, there is no particular limitation on any compound that can promote the crystallization of acrylic resin compositions. Examples include sorbitol-based nucleating agents, phosphorus-based nucleating agents, carboxylic acid metal salt-based nucleating agents, polymer nucleating agents, and inorganic compounds other than barium sulfate and talc mentioned above. From the perspective of excellent transparency and rigidity, sorbitol-based nucleating agents, phosphorus-based nucleating agents, and polymer nucleating agents are preferred as nucleating agents.

[0267] As nucleating agents for sorbitol-based compounds, for example, nonitol 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene], 1,3,2,4-dibenzyl sorbitol, 1,3,2,4-di-(p-methylbenzyl)sorbitol, and 1,3-p-chlorobenzyl-2,4-p-methylbenzyl sorbitol can be used.

[0268] Examples of phosphorus-based nucleating agents include sodium bis(4-tert-butylphenyl) phosphate, potassium bis(4-tert-butylphenyl) phosphate, sodium 2,2'-ethylene-bis(4,6-di-tert-butylphenyl) phosphate, sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphate, and aluminum bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxophosphatacyclo-6-oxide) hydroxide.

[0269] Examples of carboxylic acid metal salt nucleating agents include aluminum p-tert-butylbenzoate, aluminum adipic acid, and sodium benzoate.

[0270] Branched α-olefin polymers are preferred as polymer nucleating agents. Examples of branched α-olefin polymers include homopolymers of 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; or copolymers thereof, and copolymers thereof with other α-olefins. Polymers of 3-methyl-1-butene are particularly preferred from the perspectives of transparency, low-temperature impact resistance, good rigidity, and economy.

[0271] Examples of inorganic compounds include aluminum foil and calcium carbonate.

[0272] Among these nucleating agents, from the perspectives of transparency, low-temperature impact resistance, rigidity, and low odor, the preferred options are 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol, bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxophosphatacyclo-6-oxide)aluminum hydroxide, and 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium.

[0273] Relative to 100 parts by mass of the above-mentioned propylene polymer (A), the above-mentioned ethylene / α-olefin copolymer (B) and the above-mentioned polymer (C), the nucleating agent content is 0.1 to 0.6 parts by mass, preferably 0.15 to 0.5 parts by mass, and more preferably 0.2 to 0.4 parts by mass.

[0274] Furthermore, these nucleating agents can be a single type or in combination of two or more types.

[0275] Nucleating agents can be synthesized or are commercially available. Examples of commercially available products include MilladNX8000 (trade name, manufactured by Milliken) (1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol), ADK STAB NA-11 (trade name, manufactured by ADEKA) (2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium salt), and ADK STAB NA-21 (trade name, manufactured by ADEKA) (a nucleating agent containing bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxophosphatacyclo-6-oxide)aluminum hydroxide as the main component).

[0276] The acrylic resin composition contains a nucleating agent, and the molded articles obtained from the acrylic resin composition have excellent rigidity and transparency.

[0277] [Acrylic resin composition] In the propylene-based resin composition, preferably, the content of the propylene polymer (A) is 40 to 75 parts by mass, the content of the ethylene / α-olefin copolymer (B) is 5 to 30 parts by mass, and the content of the polymer (C) is 10 to 30 parts by mass (wherein, the total of (A), (B), and (C) is 100 parts by mass). Relative to the total of 100 parts by mass of (A), (B), and (C), the content of barium sulfate is 5 to 10 parts by mass, the content of talc is 1 to 5 parts by mass, and the content of the nucleating agent is 0.1 to 0.6 parts by mass. More preferably, in the propylene-based resin composition, the content of the propylene polymer (A) is 50 to 74 parts by mass, the content of the ethylene / α-olefin copolymer (B) is 6 to 24 parts by mass, and the content of the polymer (C) is 15 to 25 parts by mass (wherein, the total content of the propylene polymer (A), the ethylene / α-olefin copolymer (B), and the propylene homopolymer (C) is set to 100 parts by mass).

[0278] Furthermore, the propylene resin composition may also contain components other than the aforementioned propylene polymer (A), ethylene / α-olefin copolymer (B), polymer (C), barium sulfate, talc, and nucleating agent (hereinafter also referred to as "other components"), without prejudice to the purpose of the present invention.

[0279] Other components may include: neutralizers, antioxidants, heat stabilizers, weathering agents, lubricants, UV absorbers, antistatic agents, antiblocking agents, antifogging agents, antibubbling agents, dispersants, flame retardants, antibacterial agents, fluorescent whitening agents, crosslinking agents, crosslinking aids and other additives; colorants such as dyes and pigments; fillers other than barium sulfate and talc (e.g., mica); resins other than the aforementioned propylene polymers (A), ethylene / α-olefin copolymers (B) and polymers (C).

[0280] Furthermore, the acrylic resin composition preferably does not contain zinc chelating compounds represented by the following general formula [I]. In the formula, Ar1 and Ar2 represent arylene, alkylarylene, cycloalkylarylene, arylarylene, or aralkylarylene, respectively.

[0281] The acrylic resin composition preferably does not contain shell hydrates with an average particle size of 0.1 to 30 μm.

[0282] When the propylene resin composition contains other components, the content of the other components is preferably in the range of 0.01 to 5 parts by mass relative to a total of 100 parts by mass of the propylene polymer (A), ethylene / α-olefin copolymer (B), and polymer (C).

[0283] Furthermore, the melt flow rate (MFR) of the acrylic resin composition, measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg, is preferably 20 to 100 g / 10 min, more preferably 30 to 80 g / 10 min, and even more preferably 40 to 70 g / 10 min. When the melt flow rate (MFR) is within the above range, the flowability of the acrylic resin composition when forming containers, etc., is excellent, and therefore preferred.

[0284] The melt flow rate (MFR) of the acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) can be adjusted by appropriately selecting the melt flow rate (MFR) of the acrylic polymer (A) contained in the acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) or the melt flow rate (MFR) of the ethylene / α-olefin copolymer (B) (ASTM D-1238, test temperature 190°C, load 2.16 kg).

[0285] In addition, as a method to adjust the melt flow rate (MFR) of an acrylic resin composition, one example is the use of organic peroxides during melt blending of the components in a mixer. By adding organic peroxides during melt blending or increasing the amount of organic peroxides added during melt blending, the melt flow rate (MFR) of the acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) can be increased.

[0286] As for the aforementioned organic peroxides, there are no particular limitations, but examples include benzoyl peroxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl isopropyl carbonate peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexyn-3, tert-butyl dipyridyl peroxide, tert-butyl peroxide-3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane, 2,5-di... Organic peroxides such as methyl-2,5-di(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylisopropylphenyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, p-isopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, or 2,5-dimethyl-2,5-di(hydroperoxy)hexane.

[0287] Furthermore, among these, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane and 1,3-bis(tert-butylperoxide isopropyl)benzene are more preferred as organic peroxides.

[0288] When using organic peroxide, the amount of organic peroxide used is preferably in the range of 0.005 to 0.05 parts by mass relative to a total of 100 parts by mass of propylene polymer (A), ethylene / α-olefin copolymer (B) and polymer (C).

[0289] There are no particular limitations on the manufacturing method of acrylic resin compositions. For example, methods that use a mixer to melt-mix the components in the composition to manufacture acrylic resin compositions can be listed. There are no particular limitations on the mixer, and examples include single-screw mixing extruders, multi-screw mixing extruders, kneaders, Bamberley mixers, Henschel mixers, etc.

[0290] As for the conditions for melt mixing, there are no particular restrictions as long as the melt resin does not deteriorate due to shearing, heating temperature, or exothermic reactions during mixing. From the perspective of preventing melt resin deterioration, it is preferable to set an appropriate heating temperature or add antioxidants or heat stabilizers.

[0291] The molded articles involved in this invention are formed from the above-mentioned acrylic resin composition.

[0292] There are no particular restrictions on the molding method for the molded body, and well-known molding techniques can be used. Examples of molding methods include injection molding, injection stretch blow molding, compression molding, injection compression molding, T-die molding, stretch film molding, blown film molding, sheet molding, calendering, pneumatic molding, vacuum forming, tube forming, profile extrusion molding, hollow molding, and lamination molding.

[0293] The above-mentioned molded body (preferably a container, such as a food packaging container) is preferably an injection molded body or an injection stretch blow molded body.

[0294] As an injection molding method, one example is the molding method using an injection molding machine. First, an acrylic resin composition is introduced into the hopper of the injection equipment. The acrylic resin composition is then fed into a barrel heated to approximately 200–250°C, where it is mixed and plasticized to form a molten state. This molten state is then achieved under high pressure and high speed (maximum pressure 700–1500 kg / cm²). 3 The acrylic resin composition is injected from a nozzle into a mold sealed by a mold-closing device, where the temperature is adjusted to 5–50°C, preferably 30–50°C, using cooling water or warm water. The injected acrylic resin composition is cooled and cured by cooling from the mold, and the mold is opened using the mold-closing device to obtain the molded product.

[0295] Additionally, in injection stretch blow molding, for example, an acrylic resin composition is introduced into the hopper of an injection molding machine, and the resin is fed into a barrel heated to approximately 200°C to 250°C, where it is mixed and plasticized to form a molten state. This is then subjected to a maximum pressure of 700–1500 kg / cm². 3 The material is injected from the nozzle into a mold sealed by a mold-closing device at a temperature of 5-50°C, preferably 10-30°C, using cooling water or warm water. It is cooled in the mold for 1.0-3.0 seconds to form a preform. The mold is then immediately opened, and the material is stretched longitudinally and oriented using a stretching bar. It is then stretched laterally and oriented by blow molding to obtain the molded product.

[0296] There are no particular limitations on the molded body obtained from the acrylic resin composition; examples include containers, appliance parts, and daily necessities. Among these, containers are preferred as molded bodies from the perspective of excellent impact resistance and rigidity, and food packaging containers are more preferred.

[0297] The molded bodies described above can be used in a wide range of applications, such as packaging containers for liquid daily necessities like shampoos, conditioners, cosmetics, detergents, and disinfectants; liquid food packaging containers for beverages, water, and condiments; solid food packaging containers for jelly, pudding, and yogurt; other pharmaceutical packaging containers; industrial liquid packaging containers; molded bodies for conveyor equipment or household appliances; and more.

[0298] Among them, considering its superior thin-walled, lightweight, and transparent properties compared to existing molded bodies, as well as its reduced odor, this molded body is suitable for use in entrusted equipment or household appliances, and is also suitable for use as a container.

[0299] Example The present invention will be described in more detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0300] The physical properties of the propylene polymer (A) and the ethylene / α-olefin copolymer (B) were determined by the following method.

[0301] <Components insoluble in n-decane (D) insol ) and components soluble in n-decane (D sol The content of ) > D of propylene polymer (A) insol and D sol The content of each was determined by the following methods.

[0302] 200 mL of n-decane was added to 5 g of a sample of propylene polymer (A), and the mixture was heated at 145 °C for 30 minutes to dissolve it, yielding solution (1). Then, solution (1) was cooled to room temperature (25 °C) over approximately 2 hours and left at 25 °C for 30 minutes to obtain solution (2) containing precipitate (α). The precipitate (α) was then filtered from solution (2) using a filter cloth with a mesh size of approximately 15 μm. After drying the precipitate (α), its mass was determined. The mass of the precipitate (α) was divided by the mass of the sample (5 g), and the resulting value was taken as the component insoluble in n-decane (D). insol The content of ) was determined. Additionally, the solution (2) after filtering out the precipitate (α) was added to approximately three times the volume of acetone in solution (2) to precipitate the components dissolved in n-decane, resulting in precipitate (β). The precipitate (β) was then filtered out using a glass filter (G2, mesh size approximately 100–160 μm), dried, and its mass was measured. The mass of the precipitate (β) at this point was divided by the sample mass (5 g), and the resulting value was taken as the component soluble in n-decane (D). sol The content of ). In addition, in the above embodiments, no residue was observed on the filtrate side after the precipitate (β) was filtered out, even after concentration, drying and solidification.

[0303] <intrinsic viscosity [η] sol ] and intrinsic viscosity [η insol > The above D of propylene polymer (A) sol The intrinsic viscosity [η] of tetrahydronaphthalene measured at 135 °C. sol The determination is as follows.

[0304] Using the above method to obtain D insol and D sol The precipitate (β) obtained at a certain content was used as the sample. Approximately 25 mg of this sample was dissolved in 25 mL of tetrahydronaphthalene, and the relative viscosity η was measured in an oil bath at 135 °C. sp After diluting the tetrahydronaphthalene solution with 5 mL of tetrahydronaphthalene solvent, the relative viscosity η was measured using the same procedure. sp This dilution operation is repeated twice more to calculate the concentration (C) extrapolated to 0, resulting in η. sp The value of / C is used as the intrinsic viscosity, and this value is used as D. sol The intrinsic viscosity [η] of tetrahydronaphthalene measured at 135 °C. sol ] .

[0305] In addition, regarding the above D of the propylene polymer (A) insol The intrinsic viscosity [η] of tetrahydronaphthalene measured at 135 °C. insol In addition to using the method to obtain D, insol and D sol Apart from the precipitate (α) obtained when the content is [a certain value], which is used as a sample, the intrinsic viscosity [η] is [a certain value]. sol The determination method is obtained in the same way.

[0306] <D sol The content of ethylene-derived structural units in the content > The above D sol The content of ethylene-derived structural units in the content is based on 13 The C-NMR determination is performed and calculated as described below.

[0307] The sample uses the above method to determine D. insol and D sol The precipitate (β) was obtained at a certain content. This precipitate (β) was used as a sample and subjected to the following conditions. 13 C-NMR determination.

[0308] << 13 C-NMR measurement conditions >> - Measuring apparatus: LA400 nuclear magnetic resonance spectrometer manufactured by NEC Corporation. • Measurement mode: BCM (Bilevel Complete decoupling) • Observation frequency: 100.4MHz • Observation range: 17006.8Hz • Pulse width: C core 45° (7.8μs) • Pulse repetition time: 5 seconds • Sample tube: φ5mm • 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 size: Approximately 40 mg Based on the measured spectrum, the ratio of monomer chain distribution (triad distribution) was determined according to the following literature (1), and the D of the propylene polymer (A) was calculated. sol The mole fraction (mol%) of ethylene-derived structural units (hereinafter referred to as E (mol%)) and the mole fraction (mol%) of propylene-derived structural units (hereinafter referred to as P (mol%)) are calculated. Based on the calculated E (mol%) and P (mol%), the mass percentage of the propylene polymer is converted to % according to the following formula (Equation 1), and the D of the propylene polymer is calculated. sol The content (mass%) of structural units derived from ethylene (hereinafter referred to as E (mass%)).

[0309] Reference (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Carbon-13 NMRdetermination of monomer sequence distribution in ethylene-propylenecopolymers 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] … (Equation 1) <Mel Flow Rate (MFR)> Melt flow rates of propylene polymers (A), propylene polymers (C1), and propylene resin compositions were determined according to ASTM D-1238 (230°C, 2.16 kg load).

[0310] The melt flow rate of the ethylene / α-olefin copolymer (B) was determined according to ASTM D-1238 (test temperature 190°C, load 2.16 kg).

[0311] <Density of ethylene / α-olefin copolymer (B)> The density of the ethylene / α-olefin copolymer (B) was determined as described below.

[0312] The ethylene / α-olefin copolymer (B) obtained by measuring the melt flow rate at a test temperature of 190°C with a load of 2.16 kg (ASTM D-1238) was heat-treated at 120°C for 1 hour and then slowly cooled to room temperature for 1 hour. The resulting material was used as a sample, and the density was determined by density gradient tube method.

[0313] <Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of ethylene / α-olefin copolymer (B)> The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (B) were determined using GPC under the following conditions. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were obtained by converting commercially available monodisperse standard polystyrene using calibration curves as follows.

[0314] (Measurement conditions) Apparatus: Gel permeation chromatography HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Organic solvent: o-dichlorobenzene Chromatographic columns: 2 TSKgel GMH6-HT columns and 2 TSKgel GMH6-HTL columns (all manufactured by Tosoh Corporation). Flow rate: 1.0 mL / min Sample: 0.10 mg / mL o-dichlorobenzene solution Temperature: 140℃ Molecular weight conversion: PS conversion / general correction method The general correction was calculated using the coefficients of the Mark-Houwink viscosity formula. The Mark-Houwink coefficients of PS were used with the values ​​recorded in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970)).

[0315] <Manufacturing Example A1> [Manufacturing of propylene-based polymers (A-1)] (1) Preparation of solid catalyst components After heating 95.2g of anhydrous magnesium chloride, 442mL of decane and 390.6g of 2-ethylhexanol at 130℃ for 2 hours to obtain a homogeneous solution, 21.3g of phthalic anhydride was added to the solution, and the mixture was stirred at 130℃ for 1 hour to dissolve the phthalic anhydride.

[0316] After cooling the resulting homogeneous solution to room temperature, 75 mL of the homogeneous solution was added dropwise to 200 mL of titanium tetrachloride, which was maintained at -20°C, over a period of 1 hour. After the addition was completed, the temperature of the mixture was raised to 110°C over a period of 4 hours. At 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was then stirred at this temperature for 2 hours.

[0317] After the 2-hour reaction was completed, the solid fraction was collected by hot filtration and resuspended in 275 mL of titanium tetrachloride. The mixture was then heated at 110 °C for another 2 hours. After the reaction was complete, the solid fraction was collected again by hot filtration and thoroughly washed with decane and hexane at 110 °C until no free titanium compounds were detectable in the solution.

[0318] The detection of the aforementioned free titanium compounds was confirmed using the following method. 10 mL of the supernatant from the solid catalyst composition was taken using a syringe and transferred to a 100 mL Schlenk flask with a side arm, which had been pre-purged with nitrogen. The solvent hexane was then dried using a nitrogen stream, followed by vacuum drying for 30 minutes. 40 mL of ion-exchanged water and 10 mL of 50% sulfuric acid were added, and the mixture was stirred for 30 minutes. This aqueous solution was transferred through filter paper to a 100 mL volumetric flask. Then, 1 mL of concentrated H₃PO₄ as an iron(II) ion masking agent and 5 mL of a 3% H₂O₂ aqueous solution as a titanium colorimetric reagent were added, and the volume was brought to 100 mL with ion-exchanged water. The volumetric flask was shaken, and after 20 minutes, the absorbance was observed using a UV light at a wavelength of 420 nm to detect free titanium. This process of removing and detecting free titanium continued until no absorption was observed.

[0319] The prepared solid titanium catalyst component (A) was stored in the form of a decane slurry. To investigate the catalyst composition, a portion of the slurry was dried. Regarding the composition of the obtained solid titanium catalyst component (A), titanium was 2.3% by mass, chlorine was 61% by mass, magnesium was 19% by mass, and diisobutyl phthalate (DIBP) was 12.5% ​​by mass.

[0320] (2) Preparation of prepolymer catalyst components After purging a 500 mL three-necked flask equipped with a stirrer with nitrogen, 400 mL of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and 4 g of the aforementioned solid titanium catalyst component (A) were added. The internal temperature was maintained at 20 °C, and propylene was introduced while stirring. Stirring was stopped after 1 hour, yielding a prepolymer catalyst component (B) in which 1 g of solid titanium catalyst component (A) polymerized 2 g of propylene.

[0321] (3-1) Polymerization-1 (Polymerization [Process 1]) A 10L stainless steel autoclave equipped with a stirrer was thoroughly dried. After purging with nitrogen, 6L of dehydrated heptane, 12.5mmol of triethylaluminum, and 0.6mmol of dicyclopentyldimethoxysilane were added. After purging the nitrogen in the system with propylene, hydrogen gas was introduced at 0.30MPa-G, and then propylene was introduced while stirring. After the system stabilized at an internal temperature of 80°C and a total pressure of 0.8MPa-G, 20.8mL of heptane slurry containing 0.10mmol of the aforementioned prepolymer catalyst component (B) (equivalent to titanium atoms) was added, and polymerization was carried out at 80°C for 3 hours while continuously supplying propylene.

[0322] (3-2) Polymerization-2 (Polymerization [Process 2]) After the polymerization of the propylene homopolymer is completed (after step 1 above), the internal temperature is lowered to 30°C and depressurization is performed. Then, 0.10 MPa-G of hydrogen is introduced, followed by a propylene / ethylene mixture of (4.0 L / min) / (2.4 L / min). The copolymerization of propylene and ethylene is carried out for 60 minutes at an internal temperature of 60°C and a total pressure of 0.30 MPa-G.

[0323] After the specified time, 50 mL of methanol was added to terminate the reaction, followed by cooling and depressurization. The contents were transferred to a filter tank equipped with a filter, and the mixture was heated to 60°C for solid-liquid separation. The solid fraction was then washed twice with 6 L of heptane at 60°C, followed by vacuum drying. The resulting propylene polymer (A-1) had a melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of 89 g / 10 min and a D... insol 92.02% by mass, D sol It is 7.98% by mass, [η] sol [1.77 dl / g, D] sol The content of ethylene-derived structural units in it is 30.9% by mass.

[0324] <Manufacturing Example A2> [Manufacturing of propylene-based polymers (A-2)] Except for changing the copolymerization time of propylene and ethylene in polymer-2 to 40 minutes in the manufacture of propylene polymer (A-1) (Manufacturing Example 1), polymerization was carried out in the same manner as in the manufacture of propylene polymer (A-1) (Manufacturing Example 1). The resulting propylene polymer (A-2) had a melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of 107 g / 10 min and a D... insol 93.80% by mass, D sol The intrinsic viscosity is 6.20% by mass and [η]. sol [1.77 dl / g, D] sol The content of ethylene-derived structural units in it is 30.9% by mass.

[0325] <Manufacturing Example A3> [Manufacturing of propylene polymers (A-3)] Except for changing the copolymerization time of propylene and ethylene in polymer-2 to 30 minutes in the manufacture of propylene polymer (A-1) (Manufacturing Example 1), polymerization was carried out in the same manner as in the manufacture of propylene polymer (A-1) (Manufacturing Example 1). The resulting propylene polymer (A-3) had a melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of 55 g / 10 min and a D... insol 95.80% by mass, D sol The intrinsic viscosity is 4.20% by mass and [η]. sol [1.82 dl / g, D] sol The content of ethylene-derived structural units in it is 29.2% by mass.

[0326] <Manufacturing Example A4> [Manufacturing of propylene polymers (A-4)] (1) Preparation of solid catalyst components After heating 95.2g of anhydrous magnesium chloride, 442mL of decane and 390.6g of 2-ethylhexanol at 130℃ for 2 hours to obtain a homogeneous solution, 21.3g of phthalic anhydride was added to the solution, and the mixture was stirred at 130℃ for 1 hour to dissolve the phthalic anhydride.

[0327] After cooling the resulting homogeneous solution to room temperature, 75 mL of the homogeneous solution was added dropwise to 200 mL of titanium tetrachloride, which was maintained at -20°C, over a period of 1 hour. After the addition was completed, the temperature of the mixture was raised to 110°C over a period of 4 hours. At 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was then stirred at this temperature for 2 hours.

[0328] After the 2-hour reaction was completed, the solid fraction was collected by hot filtration and resuspended in 275 mL of titanium tetrachloride. The mixture was then heated at 110 °C for another 2 hours. After the reaction was complete, the solid fraction was collected again by hot filtration and thoroughly washed with decane and hexane at 110 °C until no free titanium compounds were detectable in the solution.

[0329] Here, the detection of the aforementioned free titanium compounds was confirmed according to the following method.

[0330] Using a syringe, 10 mL of the supernatant from the above solid catalyst composition was transferred into a 100 mL Schlenk flask with a side arm, which had been pre-purged with nitrogen. The solvent hexane was then dried using a nitrogen stream, followed by vacuum drying for 30 minutes. 40 mL of ion-exchanged water and 10 mL of 50% sulfuric acid were added, and the mixture was stirred for 30 minutes. This aqueous solution was transferred through filter paper to a 100 mL volumetric flask. Then, 1 mL of concentrated H₃PO₄ as an iron(II) ion masking agent and 5 mL of 3% H₂O₂ aqueous solution as a titanium colorimetric reagent were added, and the volume was brought to 100 mL with ion-exchanged water. The volumetric flask was shaken, and after 20 minutes, the absorbance was measured using a UV spectrophotometer at a wavelength of 420 nm to detect free titanium. This process of removing and detecting free titanium continued until no absorption was observed.

[0331] The prepared solid titanium catalyst component (A) was stored in the form of decane slurry. To study the catalyst composition, a portion of the slurry was dried. Regarding the composition of the obtained solid titanium catalyst component (A), titanium was 2.3% by mass, chlorine was 61% by mass, magnesium was 19% by mass, and DIBP was 12.5% ​​by mass.

[0332] (2) Preparation of prepolymer catalyst components After purging a 500 mL three-necked flask equipped with a stirrer with nitrogen, 400 mL of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and 4 g of the aforementioned solid titanium catalyst component (A) were added. The internal temperature was maintained at 20 °C, and propylene was introduced while stirring. Stirring was stopped after 1 hour, yielding a prepolymer catalyst component (B) in which 1 g of solid titanium catalyst component (A) polymerized 2 g of propylene.

[0333] (3-1) Polymerization-3 (Polymerization [Process 1]) A 10L stainless steel autoclave equipped with a stirrer was thoroughly dried. After nitrogen purging, 6L of dehydrated heptane, 12.5mmol of triethylaluminum, and 0.6mmol of dicyclopentyldimethoxysilane were added. After purging the nitrogen system with propylene, hydrogen gas was introduced at 0.25MPa-G. Propylene and ethylene were then introduced while stirring. The introduction rate was adjusted to achieve an ethylene concentration of 0.6 mol% in the gas phase of the polymerization tank.

[0334] After the system was stabilized at an internal temperature of 80°C and a total pressure of 0.8 MPa-G, 20.8 mL of heptane slurry containing 0.10 mmol of the above-mentioned prepolymer catalyst component (B) was added, and propylene was continuously supplied while polymerization was carried out at 80°C for 3 hours.

[0335] (3-2) Polymerization-4 (Polymerization [Process 2]) After the polymerization of the propylene homopolymer is completed (after step 1 above), the internal temperature is cooled to 30°C and depressurization is performed. Then, 0.90 MPa-G of hydrogen is introduced, followed by a propylene / ethylene mixture of (4.0 L / min) / (1.4 L / min). Propylene / ethylene copolymerization is carried out for 80 minutes at an internal temperature of 60°C and a total pressure of 0.30 MPa-G (which varies depending on the amount of gas introduced).

[0336] After the specified time, 50 mL of methanol was added to terminate the reaction, followed by cooling and depressurization. The contents were then transferred to a filter tank equipped with a filter, and the mixture was heated to 60°C for solid-liquid separation. The solid fraction was then washed twice with 6 L of heptane at 60°C.

[0337] The propylene / ethylene copolymer (propylene polymer (A-1)) obtained in this manner was vacuum dried. The resulting propylene polymer (A-1) had a melt flow rate (MFR) (ASTM D-1238, test temperature 230℃, load 2.16kg) of 42g / 10min and a D... insol 88.00% by mass, D sol 12.00% by mass, intrinsic viscosity [η] sol [2.00 dl / g, D] insol The mass of the ethylene-derived structural unit in it is 0.8% by mass, D sol The mass of the ethylene-derived structural units in the mixture is 22.0% by mass.

[0338] <Manufacturing Example A5> [Manufacturing of propylene polymers (A-5)] Except for changing the copolymerization time of propylene and ethylene in polymer-4 to 60 minutes in the manufacture of propylene polymer (A-4) (Manufacturing Example 4), polymerization was carried out in the same manner as in the manufacture of propylene polymer (A-4) (Manufacturing Example 4). The resulting propylene polymer (A-5) had a melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of 46 g / 10 min and a D... insol 91.00% by mass, D sol 9.0% by mass, intrinsic viscosity [η] sol [2.00 dl / g, D] sol The content of ethylene-derived structural units in it is 22.0% by mass.

[0339] [Table 1] [Preparation of ethylene / α-olefin copolymer (B-1)] (Preparation of catalyst) 10.0 kg of silica dried at 600 °C for 10 hours and 154 L of toluene were charged into a 300 L reactor after complete nitrogen replacement to form a suspension, which was then cooled to 0 °C. Next, 23.4 L of a toluene solution of methylaluminoxane (Al = 3.02 mol / L) was added dropwise to the suspension over a period of 1 hour. The temperature of the system was maintained within the range of 0–5 °C. The reaction was continued at 0 °C for 30 minutes, then the temperature was raised to 95 °C over a period of 1.5 hours and reacted at this temperature for 4 hours. The temperature was then lowered to 60 °C, and the supernatant was removed by decane decane decane precipitation. The resulting solid was washed twice with toluene and then resuspended in 100 L of toluene, bringing the total volume to 160 L.

[0340] A 20.0 L toluene solution of bis(1,3-n-butylmethylcyclopentadienyl)zirconia dichloride (Zr = 25.6 mmol / L) was added dropwise to the resulting suspension at 35 °C over 30 minutes, and the reaction was continued at 35 °C for 2 hours. The supernatant was then removed, and the sample was washed twice with hexane to obtain a solid catalyst component containing 3.2 mg of zirconium per 1 g of solid catalyst component (1).

[0341] (Preparation of prepolymer catalyst) The prepared solid catalyst component (1) (7.0 kg) and hexane were loaded into a 350 L reactor after complete nitrogen replacement, bringing the total volume to 285 L. The system was cooled to 10 °C and then subjected to a flow rate of 8 Nm³. 3Ethylene was blown into hexane at a flow rate of / hr for 5 minutes. During this process, the system temperature was maintained at 10–15°C. Afterward, the ethylene supply was stopped, and 2.4 mol of diisobutylaluminum hydride (DIBALH) and 1.2 kg of 1-hexene were added. Once the system was sealed, it was then blown into hexane at a flow rate of 8 Nm. 3 Ethylene was resumed at a flow rate of / hr. After 15 minutes, the ethylene flow rate was reduced to 2 Nm³. 3 / hr, bringing the pressure within the system to 0.08 MPaG. During this process, the temperature within the system rises to 35°C. Afterwards, while adjusting the temperature within the system to 32–35°C, a flow rate of 4 Nm is applied. 3 Ethylene was supplied at a flow rate of / hr for 3.5 hours. During this process, the pressure in the system was maintained at 0.07–0.08 MPaG. Then, the system was purged with nitrogen, the supernatant was removed, and the system was washed twice with hexane. This yielded a prepolymer catalyst (2) in which 3g of polymer was polymerized per 1g of solid catalyst component.

[0342] (polymerization) The copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas-phase polymerization apparatus at a total pressure of 2.0 MPaG, a polymerization temperature of 80 °C, and a gas linear velocity of 0.7 m / s.

[0343] Polymerization was initiated while the prepolymer catalyst (2) prepared above was continuously supplied at a ratio of 4.1 g / hr and TIBA 5 mmol / hr. To maintain a constant gas composition during polymerization, ethylene, 1-hexene, hydrogen, and nitrogen were continuously supplied (gas composition: 1-hexene / ethylene = 0.03, hydrogen / ethylene = 4.2 × 10⁻⁶). －4 (Ethylene concentration = 71%). The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, and the density was 913 kg / m³. 3 The MFR (ASTM D-1238, test temperature 190℃, load 2.16kg) is 3.8g / 10min, and the Mw / Mn ratio is 2.6.

[0344] In addition, the obtained ethylene / 1-hexene copolymer is also referred to as ethylene / α-olefin copolymer (B-1).

[0345] [Preparation of ethylene / α-olefin copolymer (B-2)] (polymerization) The copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas-phase polymerization apparatus at a total pressure of 2.0 MPaG, a polymerization temperature of 70 °C, and a gas linear velocity of 0.7 m / s.

[0346] Polymerization was initiated while the prepolymer catalyst (2) prepared above was continuously supplied at a ratio of 4.1 g / hr and TIBA 5 mmol / hr. To maintain a constant gas composition during polymerization, ethylene, 1-hexene, hydrogen, and nitrogen were continuously supplied (gas composition: 1-hexene / ethylene = 0.033, hydrogen / ethylene = 4.4 × 10⁻⁶). －4 (Ethylene concentration = 49.7%). The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, and the density was 903 kg / m³. 3 The MFR (ASTM D-1238, test temperature 190℃, load 2.16kg) is 3.8g / 10min, and the Mw / Mn ratio is 2.6.

[0347] In addition, the resulting ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-2).

[0348] [Preparation of ethylene / α-olefin copolymer (B-3)] Except in the manufacturing (polymerization) of the aforementioned ethylene / α-olefin copolymer (B-1), the gas composition is changed to 1-hexene / ethylene = 0.038 and hydrogen / ethylene = 4.2 × 10⁻⁶. －4 Except for an ethylene concentration of 40.4%, the process was the same as that used to produce the ethylene / α-olefin copolymer (B-1) to obtain the ethylene / 1-hexene copolymer. The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, and the density was 890 kg / m³. 3 The MFR (ASTM D-1238, test temperature 190℃, load 2.16kg) is 3.8g / 10min, and the Mw / Mn is 2.0.

[0349] In addition, the obtained ethylene / 1-hexene copolymer is also referred to as ethylene / α-olefin copolymer (B-3).

[0350] [Example 1] Compared to the above-prepared propylene copolymer (A-1) 60.5 parts by weight, ethylene / α-olefin copolymer (B-1) 20.1 parts by weight, propylene polymer (C1) (homogeneous polypropylene, brand: J106G, manufactured by Priman Polymer Co., Ltd.) 19.4 parts by weight, and a total of 100 parts by weight of propylene copolymer (A-1), ethylene / α-olefin copolymer (B-1) and propylene polymer (C), 6 parts by weight of precipitating barium sulfate (precipitating barium sulfate, grade "300", manufactured by Sakai Chemical Industry Co., Ltd.) and talc (product name: HI-FILLER) were mixed in a Henschel mixer. 5000PJ (manufactured by Matsumura Sangyo Co., Ltd.) 3 parts by weight, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol (trade name: Millad NX8000, manufactured by Milliken Co., Ltd.) 0.20 parts by weight as a nucleating agent, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate sodium (ADKSTAB) A acrylic resin composition was prepared by comprising 0.10 parts by weight of NA-11 (manufactured by ADEKA), 0.10 parts by weight of tris(2,4-di-tert-butylphenyl) phosphite as an additive, calcium stearate as a neutralizing agent, 0.05 parts by weight of pentaerythritol tetra(3-3,5-di-tert-butyl-4)hydroxyphenyl propionate as an additive, 0.15 parts by weight of tris(2,4-di-tert-butylphenyl) phosphite as a phosphorus-based antioxidant, and 0.10 parts by weight of calcium stearate as a neutralizing agent.

[0351] The obtained composition was melt-blended using a twin-screw extruder (model: TEM-35) manufactured by Toshiba Corporation under the following conditions to obtain a stock.

[0352] (Twin-screw extruder conditions) • Screw speed 250 rpm • Resin temperature 200℃ The obtained stock was water-cooled and then cut into granules using a granulator to obtain acrylic resin composition granules. Using the obtained granules, the melt flow rate (MFR) of the acrylic resin composition was determined according to the following method (ASTM D-1238, test temperature 230°C, load 2.16 kg). The melt flow rate (MFR) of the acrylic resin composition obtained in Example 1 (ASTM D-1238, test temperature 230°C, load 2.16 kg) was 41 g / 10 min. The results are shown in Table 2.

[0353] Next, using an electric injection molding machine with a clamping force of 110 tons (manufactured by Nissei Resin Kogyo Co., Ltd., model: NEX110-12E), the above-mentioned granules were injection molded at a barrel temperature of 200°C and a mold temperature of 40°C to produce test pieces of the test piece type (type A) as described in ISO 527-2. The obtained test pieces were used for testing tensile modulus of elasticity and Charpy impact testing.

[0354] Using an electric injection molding machine with a clamping force of 100 tons (Fanuc, AutoShot T series 100D model), the granules were injected and molded at a barrel temperature of 200°C and a mold temperature of 40°C to obtain a square test piece for gloss testing with a length of 129 mm, a width of 119 mm, and a thickness of 2 mm.

[0355] Density, tensile modulus of elasticity, Charpy impact test, gloss, and anti-whitening test were determined using each test piece. These results are shown in Table 2.

[0356] 〔evaluate〕 The physical properties of propylene polymers (A), ethylene / α-olefin copolymers (B), or propylene resin compositions were determined according to the methods described below. The results are shown in Table 2 (Examples) and Table 4 (Comparative Examples).

[0357] <Rigidity> The tensile modulus of elasticity was determined using the test pieces prepared in the various examples and comparative examples according to the tensile modulus of elasticity test method specified in ISO 527-2. The tensile test was conducted at a temperature of 23°C and a test speed of 1 mm / min using a Strograph V10-C testing machine manufactured by Toyo Seiki Co., Ltd.

[0358] Using the tensile modulus of elasticity as an indicator of rigidity, it can be said that the larger the value of the tensile modulus of elasticity, the better the rigidity. It is also known that since a larger value of the tensile modulus of elasticity means better rigidity, it also means better heat resistance.

[0359] Low-temperature impact resistance Using the Charpy impact test pieces prepared in the various examples and comparative examples, the Charpy impact strength at a test temperature of 0°C (hereinafter also referred to as "low-temperature Charpy impact strength") was measured according to the Charpy impact test method specified in JIS K7111. Furthermore, it can be said that the higher the value of the low-temperature Charpy impact strength, the better the low-temperature impact resistance.

[0360] <Glossiness> According to the gloss test method specified in JIS Z 8741, the gloss of the square plate test pieces prepared in each example and comparative example was measured under the condition of a measurement angle of 60°. The measurement result of gloss is used as an indicator of gloss. That is to say, it can be said that the higher the gloss value (%), the better the gloss.

[0361] <Pearl-toned luster> Using an electric injection molding machine with a clamping force of 100 tons (Fanuc, AutoShot T series 100D model), the granules obtained in each example and comparative example were injection molded at a barrel temperature of 200°C and a mold temperature of 40°C to produce square test pieces for pearl color testing with a length of 129 mm, a width of 119 mm, and a thickness of 2 mm.

[0362] Place the square test piece used for the pearl hue test under a fluorescent lamp for visual observation, and evaluate the pearl hue according to the following evaluation criteria.

[0363] -Evaluation Criteria- A… confirmed pearlescent tone.

[0364] B… Pearl tone not confirmed.

[0365] <Anti-albinism> Using an electric injection molding machine (Fanuc, AutoShot T-series 100D model) with a clamping force of 100 tons, the granules obtained in the various examples and comparative examples were injection molded at a barrel temperature of 200°C and a mold temperature of 40°C to obtain square test pieces for whitening resistance testing with a length of 129 mm, a width of 119 mm, and a thickness of 2 mm. The square test pieces were folded by hand with both sides overlapping, and then allowed to return to their initial state. The appearance of the test pieces was then visually observed, and the whitening resistance was evaluated according to the following evaluation criteria.

[0366] -Evaluation Criteria- A… The appearance has not been confirmed to be whitened, or the appearance has been confirmed to be slightly whitened but does not affect the level of usability.

[0367] B…The appearance shows obvious whitening, which affects its practicality.

[0368] [Example 2] Except for replacing the propylene polymer (A-1) with propylene polymer (A-2) in Example 1, the preparation of the propylene resin composition was carried out in the same manner as in Example 1, and granulation was performed. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the propylene resin composition obtained in Example 2 was 45 g / 10 min. Furthermore, test pieces were prepared from the granules obtained in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2.

[0369] [Example 3] Except that the propylene polymer (A-1) was replaced with propylene polymer (A-3) in Example 1, the procedure was the same as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the propylene resin composition obtained in Example 2 was 34 g / 10 min. Furthermore, test pieces were prepared from the granules obtained in the same manner as in Example 1, and each evaluation was performed. The evaluation results are shown in Table 2.

[0370] [Example 4] Except for changing the composition in Example 1 to 71.0 parts by weight of propylene polymer (A-4) and 9.6 parts by weight of ethylene / α-olefin copolymer (B-2), the preparation of the propylene resin composition was carried out in the same manner as in Example 3. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the propylene resin composition obtained in Example 6 was 32 g / 10 min. Furthermore, test pieces were prepared from the granules obtained in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2.

[0371] [Example 5] Except for using 72.6 parts by weight of propylene polymer (A-5) and 8.0 parts by weight of ethylene / α-olefin copolymer (B-3), the propylene resin composition was prepared in the same manner as in Example 3. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the propylene resin composition obtained in Example 6 was 40 g / 10 min. Furthermore, test pieces were prepared from the granules obtained in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2.

[0372] [Example 6] Except that the proportions of the propylene polymer (A-1) and the ethylene / α-olefin copolymer (B-3) in Example 1 were changed to those listed in Table 2, and the propylene polymer (C1) was omitted, the preparation of the propylene resin composition was carried out in the same manner as in Example 1. Furthermore, test pieces were prepared from the granules obtained in the same manner as in Example 1, and each evaluation was performed. The evaluation results are shown in Table 2.

[0373] [Table 2] [Comparative Example 1] Except that talc was not used in Example 1, the preparation of the acrylic resin composition and the fabrication of test pieces were carried out in the same manner as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the obtained acrylic resin composition was 41 g / 10 min. The results using the obtained test pieces are shown in Table 4.

[0374] Comparative Example 1 does not contain talc, therefore its pearlescent appearance is inferior to that of the molded articles obtained from the acrylic resin compositions of Examples 1-6.

[0375] [Comparative Example 2] Except that no precipitating barium sulfate was used in Example 1, the preparation of the acrylic resin composition and the production of test pieces were carried out in the same manner as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the obtained acrylic resin composition was 41 g / 10 min. The results are shown in Table 4. Comparative Example 2 did not contain precipitating barium sulfate, therefore the pearlescent appearance was inferior to that of the molded bodies obtained from the acrylic resin compositions of Examples 1-6.

[0376] [Comparative Example 3] Except that homopolymer polypropylene (manufactured by Priman Polymers Co., Ltd., product number: J105G) was used instead of propylene polymer (A-1) in Example 1, the preparation of the propylene resin composition and the production of test pieces were carried out in the same manner as in Example 1. The physical properties of homopolymer polypropylene are shown in Table 3.

[0377] The melt flow rate (MFR) of the obtained acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) was 9 g / 10 min. The physical properties and evaluation results are shown in Table 4. Comparative Example 3 used homopolymer polypropylene, therefore its low-temperature impact strength was inferior to that of the molded bodies obtained from the acrylic resin compositions of Examples 1–6.

[0378] [Comparative Example 4] Except that in Example 1, random polypropylene (manufactured by Priman Polymers Co., Ltd., product number: J246M) was used instead of the propylene polymer (A-1), the preparation of the propylene resin composition and the production of test pieces were carried out in the same manner as in Example 1. The physical properties of the random polypropylene are shown in Table 3.

[0379] The melt flow rate (MFR) of the obtained acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) was 30 g / 10 min. The physical properties and evaluation results are shown in Table 4. Comparative Example 4 used atactic polypropylene, therefore its stiffness (tensile modulus of elasticity) and low-temperature impact strength were inferior to the molded bodies obtained from the acrylic resin compositions of Examples 1–6.

[0380] [Comparative Example 5] Except that in Example 1, block polypropylene (manufactured by Priman Polymers Co., Ltd., product number: J707G) was used instead of propylene polymer (A-1), the preparation of the propylene resin composition and the production of test pieces were carried out in the same manner as in Example 1. The physical properties of the block polypropylene are shown in Table 3.

[0381] The melt flow rate (MFR) of the obtained acrylic resin composition (ASTM D-1238, test temperature 230°C, load 2.16 kg) was 23 g / 10 min. Other physical properties and evaluation results are shown in Table 4. Comparative Example 5 used block polypropylene, therefore the gloss and whitening resistance were worse than the molded articles obtained from the acrylic resin compositions of Examples 1-6.

[0382] [Comparative Example 6] Except that talc was not used in Example 1 and the acrylic polymer (A-1) was replaced with acrylic polymer (A-2), the preparation of the acrylic resin composition and the production of test pieces were carried out in the same manner as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the obtained acrylic resin composition was 63 g / 10 min. Other physical properties and evaluation results are shown in Table 4. Comparative Example 6 did not contain talc, and the content of barium sulfate exceeded 10 parts by mass relative to the total of 100 parts by mass of polymer (A), copolymer (B), and polymer (C). Therefore, the pearlescent appearance was worse than that of the molded bodies obtained from the acrylic resin compositions of Examples 1-6. Furthermore, the density of Comparative Example 6 exceeded 1000 kg / m³. 3 Its specific gravity is also worse than that of the molded articles obtained from the acrylic resin compositions of Examples 1-6.

[0383] [Comparative Example 7] Except for the absence of precipitating barium sulfate in Example 1 and the substitution of propylene polymer (A-2) for propylene polymer (A-1), the preparation of the propylene resin composition and the fabrication of test pieces were carried out in the same manner as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the obtained propylene resin composition was 63 g / 10 min. Other physical properties and evaluation results are shown in Table 4.

[0384] Comparative Example 7 did not contain barium sulfate, and the talc content exceeded 5 parts by mass relative to the total of 100 parts by mass of polymer (A), copolymer (B), and polymer (C). Therefore, the pearlescent appearance was inferior to the molded articles obtained from the acrylic resin compositions of Examples 1-6. Furthermore, the density of Comparative Example 7 exceeded 1000 kg / m³. 3 Its specific gravity is also worse than that of the molded articles obtained from the acrylic resin compositions of Examples 1-6.

[0385] [Comparative Example 8] Except for the absence of precipitating barium sulfate and talc in Example 1, the preparation of the acrylic resin composition and the fabrication of test pieces were carried out in the same manner as in Example 1. The melt flow rate (MFR) (ASTM D-1238, test temperature 230°C, load 2.16 kg) of the obtained acrylic resin composition was 57 g / 10 min. Other properties and evaluation results are shown in Table 4. Comparative Example 8 did not contain precipitating barium sulfate and talc, therefore its stiffness (tensile modulus of elasticity) and pearlescent color were inferior to those of the molded pieces obtained from the acrylic resin compositions of Examples 1-6.

[0386] [Table 3] [Table 4] As shown in Tables 2 and 4, compared with the molded articles obtained from the acrylic resin compositions of Comparative Examples 1 to 8, the molded articles obtained from the acrylic resin compositions of Examples 1 to 6 have a pearl-like appearance and excellent gloss, low-temperature impact resistance and whitening resistance.

Claims

1. A acrylic resin composition, characterized in that, The content of propylene polymer (A) that meets the following conditions (A1) to (A5) is 40 to 85 parts by mass. The content of ethylene / α-olefin copolymer (B) that meets the following requirements (B2) and (B3) is 5 to 30 parts by weight. The content of polymer (C) is 0 to 30 parts by mass, and polymer (C) is at least one of propylene homopolymer and propylene / α-olefin random copolymer in which the content of structural units derived from α-olefins is less than 1.0% by mass relative to the total number of structural units of the copolymer. The total content of (A), (B), and (C) is 100 parts by mass. Relative to a total of 100 parts by mass of (A), (B), and (C), the content of barium sulfate is 5-10 parts by mass, the content of talc is 1-5 parts by mass, and the content of nucleating agent is 0.1-0.6 parts by mass. (A1): The component D of the propylene polymer (A) that is insoluble in n-decane. insol The component D, which is 88-96% by mass, is soluble in n-decane. sol The content is 4-12% by mass, of which D insol With D sol The total content is set at 100% by mass; (A2): The D sol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. sol The concentration is 1.5–2.5 dl / g; (A3): The D sol The content of ethylene-derived structural units in D relative to the content of D sol 100% by mass is 20-40% by mass; (A4): The D insol The intrinsic viscosity [η] in tetrahydronaphthalene, measured at 135 °C. insol The concentration was 0.8–1.3 dl / g; (A5): The melt flow rate (MFR) of propylene polymer (A) measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg is 35–170 g / 10 min; (B2): The density of the ethylene / α-olefin copolymer (B) is 886–920 kg / m³. 3 ; (B3): The melt flow rate (MFR) of ethylene / α-olefin copolymer (B), measured according to ASTM D-1238 at a test temperature of 190°C and a load of 2.16 kg, is 0.5 to 50 g / 10 minutes.

2. The acrylic resin composition according to claim 1, characterized in that, The ethylene / α-olefin copolymer (B) also satisfies the following requirement (B1'). (B1'): The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) of the ethylene / α-olefin copolymer (B) as determined by gel permeation chromatography (GPC) is less than 3.

0.

3. The acrylic resin composition according to claim 1, characterized in that, The ethylene / α-olefin copolymer (B) also satisfies the following requirement (B1). (B1): Ethylene / α-olefin copolymer (B) is an ethylene / α-olefin copolymer obtained by polymerization using a single-site catalyst.

4. The acrylic resin composition according to any one of claims 1 to 3, characterized in that, The content of the propylene polymer (A) is 40-75 parts by weight. The content of the ethylene / α-olefin copolymer (B) is 5 to 30 parts by weight. The content of the polymer (C) is 10 to 30 parts by weight. The total content of (A), (B) and (C) is 100 parts by mass.

5. The acrylic resin composition according to any one of claims 1 to 3, characterized in that, The polymer (C) has a melt flow rate (MFR) of 0.5 to 50 g / 10 minutes, as measured by ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg.

6. The acrylic resin composition according to any one of claims 1 to 3, characterized in that, The propylene resin composition has a melt flow rate (MFR) of 20–100 g / 10 min, measured according to ASTM D-1238 at a test temperature of 230°C and a load of 2.16 kg.

7. A molded body, characterized in that, It is formed from the acrylic resin composition according to any one of claims 1 to 3.

8. The molded article as described in claim 7, characterized in that, It is an injection-molded part or an injection stretch blow-molded part.

9. The molded article as described in claim 7, characterized in that, It is a molded body for use in entrusted equipment or household appliances.

10. The molded article as described in claim 7, characterized in that, It is a container.

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