Thermoplastic elastomer composition, molded article thereof, and its applications

Abstract

The present invention addresses the problem of providing a highly transparent thermoplastic elastomer composition that can be used suitably for purposes such as vehicle interior coverings without harming the appearance (designability such as texture moldability) and moldability of conventional vehicle interior coverings.　The thermoplastic elastomer composition includes 100 mass parts of an ethylene-α-olefin-conjugated polyene copolymer (A), 20-5,000 mass parts of a soft propylene copolymer (B) having a melting point (TmB) that is not observed or is less than 115°C, 10-500 mass parts of a crystalline polyolefin (C) having a melting point (TmC) of 115°C or higher, 0-70 mass parts of a softener (D), and 0.01-10 mass parts of a crosslinking agent (E), and the soft propylene copolymer (B) also satisfies all of the following requirements (b-1)-(b-2).　(b-1) Contains 90-50 mol% of structural units derived from propylene, 0-30 mol% of structural units derived from 1-butene, and 5-30 mol% of structural units derived from ethylene.　(b-2) The molecular weight distribution (Mw / Mn), as determined by gel permeation chromatography (GPC), falls within the range of 1.0-3.5.

Description

[Technical Field]

[0001] This invention relates to thermoplastic elastomer compositions, molded articles thereof, and applications thereof. [Background technology]

[0002] In the passenger compartment of an automobile, interior upholstery materials such as decorative panels that have a leather-like appearance are sometimes used to create a sense of luxury. Furthermore, in recent automobiles, various display devices and functional components are provided on the instrument panel in the driver's seat. For example, there are traditional gauges such as the speedometer, tachometer, and fuel gauge, as well as a wide variety of display devices and controls such as switches for the air conditioner, windows, door locks, etc., the display and control units for the car navigation system, external monitors, lighting, and decorative parts.

[0003] When display devices or control panels are installed beneath the interior surface material, the interior surface material is required to have sufficient transparency to allow the display projected onto the decorative panel to be visible when the light source of the display device or control panel is illuminated, while simultaneously possessing a high level of design aesthetics (such as a sense of luxury) when the light source is not emitting light (non-illuminating).

[0004] Patent Document 1 discloses a thermoplastic elastomer composition for weatherstrip applications, comprising 10 to 60 parts by weight of a non-crosslinked crystalline polyolefin resin (A), 1 to 20 parts by weight of a propylene-1-butene-ethylene random copolymer (B), 89 to 20 parts by weight of an ethylene-α-olefin-non-conjugated polyene copolymer rubber (C) consisting of ethylene, α-olefins having 3 to 20 carbon atoms, and non-conjugated polyenes, which is partially or entirely crosslinked, and a softening agent (D).

[0005] Patent Document 2 discloses a thermoplastic resin composition having low viscosity and excellent moldability, comprising a thermoplastic elastomer resin (A), a polyolefin resin (B), a polypropylene resin (C), and an oil (D).

[0006] Patent Document 3 discloses a thermoplastic elastomer composition that is crosslinked by mixing 1 to 98 parts by weight of isotactic polypropylene (A), 2 to 99 parts by weight of a propylene-ethylene (·α-olefin) random copolymer (B) containing 45 to 89 mol% of the propylene component, 10 to 25 mol% of the ethylene component, and optionally 0 to 30 mol% of component units derived from α-olefins having 4 to 20 carbon atoms, and 2 to 1900 parts by weight of an ethylene-α-olefin-non-conjugated polyene copolymer rubber (C). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2009-215356 [Patent Document 2] International Publication No. 2018 / 147391 [Patent Document 3] Japanese Patent Publication No. 2009-73912 [Overview of the project] [Problems that the invention aims to solve]

[0008] The thermoplastic elastomer compositions described in the above-mentioned Patent Documents 1 to 3 have not achieved both transparency and high design quality. Furthermore, it has become clear that greater transparency is required for the interior surface materials used in the above-mentioned conventional display devices. The inventors have investigated and found that when olefin-based thermoplastic elastomers are used as interior surface materials (especially for display devices and decorative panels), light refraction occurs due to the difference in refractive index of the components in the composition, and sufficient transparency cannot be obtained with conventional interior surface materials.

[0009] The present invention aims to provide a highly transparent thermoplastic elastomer composition and its molded articles that can be suitably used for applications such as interior surface materials without impairing the appearance (design properties such as texture moldability) and moldability of conventional interior surface materials. [Means for solving the problem]

[0010] The inventors of the present invention have intensively studied to solve the above problems. As a result, it has been found that a thermoplastic elastomer composition having the following configuration can solve the above problems, and the present invention has been completed. The present invention relates to, for example, the following [1] to [8]. [1] 100 parts by mass of an ethylene·α-olefin·non-conjugated polyene copolymer (A), The melting point (Tm , B , , C , , , , , , ) is not observed or is less than 115°C, 10 to 5,000 parts by mass of a soft propylene-based copolymer (B), The melting point (Tm C ) is 115°C or higher, 10 to 500 parts by mass of a crystalline polyolefin (C), 0 to 200 parts by mass of a softening agent (D), 0.01 to 10 parts by mass of a crosslinking agent (E) and a thermoplastic elastomer composition. [2] The thermoplastic elastomer composition according to [1] above, wherein the soft propylene-based copolymer (B) further satisfies all of the following requirements (b-1) to (b-2). (b-1) It contains 90 to 50 mol% of structural units derived from propylene, 0 to 30 mol% of structural units derived from 1-butene, and 5 to 30 mol% of structural units derived from ethylene. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. [3] 100 parts by mass of an ethylene·α-olefin·non-conjugated polyene copolymer (A), The melting point (Tm B ) is not observed or is less than 115°C, 10 to 5,000 parts by mass of a soft propylene-based copolymer (B), The melting point (Tm C ) is 115°C or higher, 10 to 500 parts by mass of a crystalline polyolefin (C), [[ID=X]]0 to 200 parts by mass of a softening agent (D), 0.01 to 10 parts by mass of a crosslinking agent (E) and a composition obtained by dynamically crosslinking, a thermoplastic elastomer composition. [4] The thermoplastic elastomer composition according to [3], wherein at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) is crosslinked. [5] The thermoplastic elastomer composition according to [3] or [4] above, wherein the Shore A hardness (instantaneous value) (measured according to the measurement method of JIS K 6253, using three sheets of 2 mm thickness stacked together) is 40 to 100. [6] A molded article comprising the thermoplastic elastomer composition described in any of [1] to [5] above. [7] The molded article described in [6] above, which is an automotive interior surface material. [8] The molded body according to [7], wherein the automotive interior surface material is an instrument panel, door trim, armrest, or console.

[0011] Preferably, the present invention relates to, for example, the following (1) to (14). (1) 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), Melting point (Tm B ) is not observed or the temperature is below 115°C, and 20 to 5,000 parts by mass of a soft propylene copolymer (B), Melting point (Tm C ) 10 to 500 parts by mass of crystalline polyolefin (C) whose temperature is 115°C or higher, Softener (D) 0 to 70 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and Includes, The aforementioned soft propylene copolymer (B) further satisfies all of the following requirements (b-1) to (b-2), and is a thermoplastic elastomer composition: (b-1) Contains 90-50 mol% of propylene-derived constituent units, 0-30 mol% of 1-butene-derived constituent units, and 5-30 mol% of ethylene-derived constituent units. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. (2) The thermoplastic elastomer composition according to (1), wherein the crosslinking agent (E) is an organic peroxide. (3) A thermoplastic elastomer composition as described in (1) or (2), wherein the melt flow rate (according to the measurement method of JIS K 7210, 230°C, 10 kg load) is 1 g / 10 min or more and less than 80 g / 10 min. (4) A thermoplastic elastomer composition according to any one of (1) to (3), wherein at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) is crosslinked. (5) A thermoplastic elastomer composition according to any one of (1) to (4), wherein the Shore A hardness (instantaneous value) (measured according to the measurement method of JIS K 6253, using three sheets of 2 mm thickness stacked together) is 40 to 100. (6) A molded article comprising the thermoplastic elastomer composition described in any of (1) to (5). (7) The molded body described in (6), wherein the internal haze is 80% or less. (8) The molded article described in (6) or (7), wherein the total light transmittance is 83% or more. (9) A molded article described in any of (6) to (8), which is an automotive interior surface material. (10) The molded body according to (9), wherein the automotive interior surface material is an instrument panel, door trim, armrest, or console. (11) 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), Melting point (Tm B ) is not observed or the temperature is below 115°C, 10 to 5,000 parts by mass of a soft propylene copolymer (B), Melting point (Tm C ) 10 to 500 parts by mass of crystalline polyolefin (C) whose temperature is 115°C or higher, Softener (D) 0 to 200 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and A molded article comprising a thermoplastic elastomer composition containing, A display device or operating unit provided at the lower part of the molded body, A decorative panel characterized by having the following features. (12) A method for producing a thermoplastic elastomer composition, wherein the production method is 100 parts by mass of an ethylene·α-olefin·non-conjugated polyene copolymer (A), and a soft propylene copolymer (B) of which the melting point (Tm B ) is not observed or is less than 115°C, 0 to 5,000 parts by mass, and a crystalline polyolefin (C) of which the melting point (Tm C ) is 115°C or higher, 10 to 500 parts by mass, a softening agent (D) 0 to 70 parts by mass, and a crosslinking agent (E) 0.01 to 10 parts by mass are dynamically crosslinked to obtain a composition (i) in the first step, and a second step of adding 0 to 5,000 parts by mass of the soft propylene copolymer (B) to the composition (i) is included, the total amount of the soft propylene copolymer (B) added in the first step and the second step is 20 to 5,000 parts by mass, a method for producing a thermoplastic elastomer composition in which the soft propylene copolymer (B) further satisfies all of the following requirements (b-1) to (b-2): (b-1) It contains 90 to 50 mol% of structural units derived from propylene, 0 to 30 mol% of structural units derived from 1-butene, and 5 to 30 mol% of structural units derived from ethylene. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. <13> The method for producing a thermoplastic elastomer composition according to <12>, wherein the amount of the soft propylene copolymer (B) added in the first step is 0 parts by mass.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a highly transparent composition and a molded product thereof that can be suitably used for applications such as interior skin materials without impairing the appearance (design properties such as embossing moldability) and moldability of conventional interior skin materials.

Embodiments for Carrying Out the Invention

[0013] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the configurations of the embodiments described below. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit. Furthermore, when numerical ranges are listed in steps, the upper and lower limits of each numerical range can be combined in any way.

[0014] [Thermoplastic elastomer composition] The thermoplastic elastomer composition according to the present invention (hereinafter also referred to as "this composition") comprises 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A) and a melting point (Tm B 10 to 5,000 parts by mass of a soft propylene copolymer (B) whose melting point (Tm) is not confirmed or is below 115°C, and C The composition comprises 10 to 500 parts by mass of crystalline polyolefin (C) having a melting point (Tm) of 115°C or higher, 0 to 200 parts by mass of a softening agent (D), and 0.01 to 10 parts by mass of a crosslinking agent (E), preferably comprising 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A) and a melting point (Tm). B 20 to 5,000 parts by mass of a soft propylene copolymer (B) whose melting point (Tm) is not confirmed or is below 115°C, and C The composition comprises 10 to 500 parts by mass of crystalline polyolefin (C) having a temperature of 115°C or higher, 0 to 70 parts by mass of a softening agent (D), and 0.01 to 10 parts by mass of a crosslinking agent (E). The composition may contain any of these components, and may be simply a mixture of these components, or at least some of the components may be crosslinked.

[0015] <Ethylene-α-olefin-nonconjugated polyene copolymer (A)> The ethylene-α-olefin-non-conjugated polyene copolymer (A) is not particularly limited as long as it includes constituent units derived from ethylene, constituent units derived from α-olefin, and constituent units derived from non-conjugated polyene, and can be synthesized, for example, by conventionally known methods of copolymerizing ethylene, α-olefin, and non-conjugated polyene.

[0016] The ethylene-α-olefin-non-conjugated polyene copolymer (A) contained in this composition may be one type or two or more types. When the sum of the content of ethylene-derived structural units (hereinafter also referred to as "ethylene content") and the content of α-olefin-derived structural units (hereinafter also referred to as "α-olefin content") in the ethylene-α-olefin-non-conjugated polyene copolymer (A) is taken as 100 mol%, the ethylene content is preferably 50 mol% or more, more preferably 50 to 95 mol%, even more preferably 55 to 85 mol%, and particularly preferably 60 to 83 mol%, from the viewpoint that a molded article with a good molded appearance can be easily obtained.

[0017] The α-olefin is not particularly limited, but α-olefins having 3 to 20 carbon atoms are preferred. Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These α-olefins may be used individually or in combination of two or more.

[0018] The α-olefins are preferably propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene, with propylene being more preferred. When the total ethylene content and α-olefin content in the ethylene-α-olefin-non-conjugated polyene copolymer (A) is set to 100 mol%, the α-olefin content is preferably 50 mol% or less, more preferably 5 to 50 mol%, even more preferably 15 to 45 mol%, and particularly preferably 17 to 40 mol%, from the viewpoint that a molded article with a good molded appearance can be easily obtained.

[0019] The ethylene content and α-olefin content are as follows: 13This can be determined by measurement using 1C-NMR. Examples of non-conjugated polyenes include linear non-conjugated dienes, cyclic non-conjugated dienes, and trienes. One or more of these non-conjugated polyenes may be used.

[0020] Examples of chain-like non-conjugated dienes include 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-1,7-octadiene, 8-methyl-4-ethylidene-1,7-nonadienene, and 4-ethylidene-1,7-undecadienene.

[0021] Examples of cyclic non-conjugated dienes include tetrahydroindene, methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, 5-cyclohexylidene-2-norbornene, cyclopentadiene, dicyclopentadiene, cyclooctadiene, and norbornadiene.

[0022] Examples of trienes include 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nonadien, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, and 4-ethylidene-1,6-octadiene. Examples include 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadien, 7-ethyl-4-ethylidene-1,6-nonadien, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadien, 4-ethylidene-1,6-decadien, 7-methyl-4-ethylidene-1,6-decadien, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadien, and 4-ethylidene-1,7-undecadien.

[0023] Among these, preferred non-conjugated polyenes are 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, dicyclopentadiene, and 4-ethylidene-8-methyl-1,7-nonadiene, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being more preferred.

[0024] The content of non-conjugated polyene-derived constituent units in the ethylene-α-olefin-non-conjugated polyene copolymer (A) is such that the iodine value of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is preferably 1 to 50, more preferably 5 to 40, and particularly preferably 10 to 30. When the iodine value of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is within the above range, a well-balanced crosslinked thermoplastic elastomer composition can be easily obtained when the ethylene-α-olefin-non-conjugated polyene copolymer (A) is (partially) crosslinked.

[0025] Furthermore, the content of constituent units derived from non-conjugated polyenes is typically 2 to 20% by mass relative to 100% by mass of all constituent units of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0026] As for the ethylene-α-olefin-non-conjugated polyene copolymer (A), a homogeneous mixture with components (B) to (E) contained in this composition can be easily obtained, and the Mooney viscosity [ML] measured in accordance with the measurement method of ASTM D 1646-19a was obtained. 1+4 It is desirable to use a component in which the (125℃) temperature is preferably 10 to 250, and more preferably 30 to 150.

[0027] If the ethylene-α-olefin-non-conjugated polyene copolymer (A) itself is not within the Mooney viscosity range, it may be used if necessary, after being oil-expanded using a conventionally known method, for example, with an oil-expanding agent such as the following softener. As the oil-expanding agent, a petroleum-based softener such as paraffinic process oil is preferred. The amount of oil-expanding agent used in this oil-expanding process is preferably such that the Mooney viscosity of the oil-expanded product falls within the aforementioned range, for example, 0 to 150 parts by mass per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0028] The intrinsic viscosity [η] of the ethylene-α-olefin-non-conjugated polyene copolymer (A), as measured in decalin solvent at 135°C, is preferably 1 to 10 dl / g, more preferably 1.5 to 8 dl / g.

[0029] The ethylene-α-olefin-non-conjugated polyene copolymer (A) may exist in any crosslinked state in the composition, such as uncrosslinked, partially crosslinked, or fully crosslinked. If the composition contains at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) that is crosslinked, the timing of the crosslinking is not particularly limited. For example, at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) may be (dynamically) crosslinked before mixing with the flexible propylene copolymer (B), crystalline polyolefin (C), softener (D), and crosslinking agent (E) that constitute the composition, or at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) may be (dynamically) crosslinked after or while mixing with the other components that constitute the composition.

[0030] In this composition, it is preferable that at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked. When the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked, a composition and a molded article with excellent mechanical properties, heat resistance, and molded appearance can be obtained.

[0031] Furthermore, as the degree of crosslinking of the ethylene-α-olefin-non-conjugated polyene copolymer (A) increases, the compression set of molded articles produced from this composition tends to decrease. Therefore, the degree of crosslinking of the ethylene-α-olefin-non-conjugated polyene copolymer (A) can be inferred from the compression set, oil swelling rate, and effective network chain density of molded articles produced from this composition.

[0032] The content of the ethylene-α-olefin-non-conjugated polyene copolymer (A) in this composition is not particularly limited as long as it satisfies the aforementioned ratio of each component constituting the composition, in order to easily obtain a molded article with the hardness required for practical use. However, the upper limit is usually 80% by mass or less, preferably 55% by mass or less, more preferably 45% by mass or less, and even more preferably 25% by mass or less. The lower limit is usually 1% by mass or more, preferably 4% by mass or more. The ethylene-α-olefin-non-conjugated polyene copolymer (A) may be synthesized by conventionally known methods, or a commercially available product may be used.

[0033] <Soft propylene copolymer (B)> Melting point (Tm) of the soft propylene copolymer (B) according to the present invention B The melting point (Tm) of the soft propylene copolymer (B) is not observed or is below 115°C, preferably not observed or 113°C or lower, more preferably not observed or 110°C or lower, and even more preferably not observed or 108°C or lower. B If the range is within the above range, a composition and molded article with excellent mechanical properties and heat resistance can be obtained. The soft propylene copolymer (B) contained in this composition may be one type or two or more types.

[0034] The melting point of the flexible propylene copolymer (B) can be measured specifically by the method described in the examples below. The flexible propylene copolymer (B) is a propylene polymer selected from propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene-α-olefin graft copolymer, propylene-α-olefin-ethylene random copolymer, etc.

[0035] Specifically, the α-olefins mentioned above include the α-olefins described in the above section <Ethylene-α-olefin-non-conjugated polyene copolymer (A)>, with ethylene or 1-butene being preferred, and 1-butene being more preferred.

[0036] These α-olefins may be used individually or in combination of two or more types. The flexible propylene copolymer (B) further satisfies all of the following requirements (b-1) to (b-2).

[0037] (b-1) Contains 90-50 mol% of propylene-derived constituent units, 0-30 mol% of 1-butene-derived constituent units, and 5-30 mol% of ethylene-derived constituent units. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5.

[0038] Furthermore, the flexible propylene copolymer (B) according to the present invention preferably satisfies one or more of the following requirements (b-3) to (b-5), and more preferably satisfies all of requirements (b-3) to (b-5).

[0039] (b-3) The intrinsic viscosity [η] measured at 135°C in decalin solvent is in the range of 0.01 to 10 dl / g. (b-4) Triad tacticity (mm fraction) is 85% or higher. (b-5) The heat of fusion (ΔH) is not observed or is less than 50 J / g. The following explains each of these requirements.

[0040] ≪(b-1) Content of constituent units≫ The flexible propylene copolymer (B) has high transparency and allows for easy production of molded articles with good molded appearance. Therefore, when the constituent units of the flexible propylene copolymer (B) are considered as 100 mol%, it preferably contains propylene-derived constituent units (hereinafter also referred to as "propylene content") in an amount of 90-50 mol%, more preferably 85-55 mol%, and even more preferably 80-65 mol%, 1-butene-derived constituent units (hereinafter also referred to as "1-butene content") in an amount of 0-30 mol%, more preferably 1-25 mol%, and even more preferably 1-20 mol%, and ethylene-derived constituent units (hereinafter also referred to as "ethylene content") in an amount of 5-30 mol%, more preferably 5-25 mol%, and even more preferably 5-23 mol%. The propylene content, 1-butene content, and ethylene content are as follows: 13 This can be determined by measurement using 1C-NMR.

[0041] ≪(b-2) Molecular weight distribution (Mw / Mn)≫ The molecular weight distribution (Mw / Mn) of the flexible propylene copolymer (B) is preferably in the range of 1.0 to 3.5, more preferably 1.5 to 3.0, and even more preferably 1.7 to 2.8. By setting the molecular weight distribution (Mw / Mn) within the above range, the moldability of the composition is improved.

[0042] In this embodiment, the molecular weight distribution (Mw / Mn) is calculated from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene equivalent, measured by gel permeation chromatography (GPC).

[0043] ≪(b-3) Intrinsic viscosity [η]≫ The intrinsic viscosity [η] of the soft propylene copolymer (B), measured at 135°C in decalin solvent, is preferably 0.01 to 10 dl / g, more preferably 0.05 to 5.0 dl / g, and even more preferably 1.0 to 4.5 dl / g. By setting the intrinsic viscosity [η] within the above range, a thermoplastic elastomer with excellent properties such as weather resistance, ozone resistance, heat aging resistance, and low-temperature characteristics can be obtained.

[0044] ≪(b-4) Triad Tacticity (mm fraction)≫ The stereoregularity of the soft propylene copolymer (B) can be evaluated by triad tacticity (mm fraction), which is preferably 85% or more, more preferably 88-98%, and even more preferably 90-95%.

[0045] Here, "mm fraction" is defined as the proportion of three head-to-tail linked propylene unit chains in a polymer chain whose methyl group branching directions are identical when represented by a surface zigzag structure. 13 It can be determined from the 1C-NMR spectrum. Specifically, the mm fraction of the flexible propylene copolymer (B) used in this invention can be determined by the method described on page 21, line 7 to page 26, line 6 of the International Publication No. 2004 / 087775.

[0046] The soft propylene copolymer (B) used in the present invention is preferably one in which the degree of crystallinity measured by DSC (differential scanning calorimetry) or X-rays does not exceed 30% from the viewpoint of transparency, more preferably 25% or less, even more preferably 20% or less, and even more preferably 10% or less.

[0047] ≪(b-5) Heat of fusion (ΔH)≫ The heat of fusion (ΔH) of the flexible propylene copolymer (B) is preferably not observed or less than 50 J / g. More preferably it is not observed or 45 J / g or less, and even more preferably not observed or 40 J / g or less. Because the flexible propylene copolymer (B) of the present invention satisfies the above range, it tends to have a low degree of crystallinity, and the thermoplastic elastomer composition containing it has excellent transparency.

[0048] There are no particular limitations on the method for producing the flexible propylene copolymer (B) in the present invention, but it can be produced in the presence of a known catalyst capable of stereoregular polymerization of olefins in an isotactic or syndiotactic structure, such as a catalyst mainly composed of a solid titanium component and an organometallic compound, or a metallocene catalyst using a metallocene compound as one component of the catalyst. Of these, it is preferable to produce it by copolymerizing propylene, 1-butene, and ethylene in the presence of a metallocene catalyst. As the metallocene catalyst, it is preferable to use, for example, the catalyst described in Examples e1 to e5 of International Publication No. 2004 / 087775, or the catalyst described in Japanese Patent Publication No. 2007-186664.

[0049] This composition contains a soft propylene copolymer (B) in an amount of 10 to 5,000 parts by mass, preferably 20 to 5,000 parts by mass, more preferably 20 to 4,000 parts by mass, even more preferably 25 to 3,000 parts by mass, even more preferably 27 to 2,500 parts by mass, and particularly preferably 30 to 2,500 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0050] This composition forms a sea-island structure with a phase consisting of an ethylene-α-olefin-non-conjugated polyene copolymer (A) and a phase consisting of a crystalline polyolefin (C). By including a flexible propylene copolymer (B) within the above range, the flexible propylene copolymer (B) becomes miscible with the crystalline polyolefin (C) phase, thereby reducing the refractive index of the crystalline polyolefin (C) phase. Therefore, it is believed that transparency is improved by reducing the refractive index difference between the ethylene-α-olefin-non-conjugated polyene copolymer (A) phase and the crystalline polyolefin (C) phase.

[0051] <Crystalline polyolefin (C)> The crystalline polyolefin (C) according to the present invention has a melting point (Tm C The melting point (Tm) of crystalline polyolefin (C) is 115°C or higher. Preferably it is 115 to 175°C, more preferably 118 to 172°C, and even more preferably 120 to 170°C. c When the above range is present, compositions and molded articles with excellent mechanical properties and heat resistance can be obtained.

[0052] The melting point of crystalline polyolefin (C) can be measured specifically by the method described in the examples below. The heat of fusion (ΔH) of the crystalline polyolefin (C) according to the present invention is preferably 50 J / g or more, more preferably 60 J / g or more, and even more preferably 70 J / g or more. The crystalline polyolefin (C) of the present invention tends to have a high degree of crystallinity because it satisfies the above range, and the thermoplastic elastomer composition containing it has excellent physical properties such as mechanical properties and heat resistance.

[0053] The method for producing the crystalline polyolefin (C) used in the present invention is not particularly limited as long as a crystalline polymer can be obtained. It is preferable to produce it by polymerizing one or more monoolefins using polymerization methods such as the gas phase method, liquid phase method, slurry method, or bulk method.

[0054] The crystalline polyolefin (C) may be a homopolymer or a copolymer. The homopolymer may have either an isotactic or syndiotactic structure. The aforementioned homopolymers are typically ethylene homopolymers, propylene homopolymers, and 1-butene homopolymers, preferably ethylene homopolymers and propylene homopolymers, and more preferably propylene homopolymers.

[0055] The copolymer is not limited as long as it is polymerized from two or more monoolefins. The copolymer structure may be random or blocky. Suitable raw material olefins include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. The number of carbon atoms is preferably 2 to 12, more preferably 2 to 6.

[0056] These α-olefins can be used individually or in combination of two or more. Examples of copolymers include propylene-ethylene random copolymer, propylene-ethylene block copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-4-methyl-1-pentene copolymer.

[0057] Representative crystalline polyolefin (C) resins are also commercially available. Examples of commercially available crystalline polyolefin (C) include Evolu [registered trademark] (manufactured by Prime Polymer Co., Ltd.), Prime Polypro [registered trademark] (manufactured by Prime Polymer Co., Ltd.), and Novatec. TM Examples include crystalline polyolefins manufactured and sold under product names such as Nippon Polypropylene Co., Ltd. and Sun Allomer [registered trademark] (manufactured by Sun Allomer Co., Ltd.).

[0058] The crystalline polyolefin (C) used in this invention plays a role in improving the fluidity and heat resistance of the composition. The crystalline polyolefin (C) preferably has a melt flow rate (MFR: ASTM D 1238-65T, 230°C, 2.16 kg load) in the range of 0.01 to 100 g / 10 min, more preferably 0.05 to 80 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably 0.5 to 30 g / 10 min.

[0059] This composition contains crystalline polyolefin (C) in an amount of 10 to 500 parts by mass, preferably 30 to 450 parts by mass, and more preferably 50 to 400 parts by mass, of ethylene-α-olefin-non-conjugated polyene copolymer (A) per 100 parts by mass.

[0060] <Softener (D)> It is preferable to use a softening agent in this composition for purposes such as adjusting the fluidity and hardness. Specific examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petrolatum; coal tar-based softeners such as coal tar and coal tar pitch; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; sub(factis); waxes such as beeswax, carnauba wax, and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and lauric acid. Examples include fatty acids or fatty acid salts such as zinc phosphate; naphthenic acid; pine oil, rosin or its derivatives; synthetic polymer softeners such as terpene resins, petroleum resins, coumarone indene resins, and atactic polypropylene; ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiocol, and hydrocarbon-based synthetic lubricants.

[0061] Among these, petroleum-based softeners, particularly process oils, are preferred. As mentioned above, the softening agent may be, for example, one that has been pre-mixed (oil-spread) with an ethylene-α-olefin-non-conjugated polyene copolymer (A), or it may be used when preparing the composition, or it may be added later when dynamically heat-treating each component to be incorporated into the composition.

[0062] This composition contains a softening agent (D) in an amount of 0 to 200 parts by mass, preferably 1 to 200 parts by mass, more preferably 20 to 200 parts by mass, even more preferably 40 to 180 parts by mass, and particularly preferably 50 to 150 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A). It is also a preferred embodiment that this composition contains a softening agent (D) in an amount of 0 to 70 parts by mass or 0 to 70.0 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A). Furthermore, this composition contains a softening agent (D) in an amount of 1 to 70 parts by mass or 1 to 70.0 parts by mass, even more preferably 20 to 70 parts by mass or 20 to 70.0 parts by mass, and particularly preferably 40 to 70 parts by mass or 40 to 70.0 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0063] When the content of the softening agent is within the aforementioned range, it tends to be easy to obtain a composition with fluidity suitable for molding, and furthermore, it tends to be easy to obtain a molded article with excellent mechanical properties, heat resistance, and heat aging resistance.

[0064] <Crosslinking agent (E)> When it is desired to partially or completely crosslink the ethylene-α-olefin-non-conjugated polyene copolymer (A) in this composition, it is preferable to use a crosslinking agent (E), especially when dynamically crosslinking an uncrosslinked composition containing each component, and a crosslinking agent (E) is used in the preparation of this composition in which at least a portion of the components are crosslinked.

[0065] The crosslinking agent (E) is not particularly limited, and conventionally known crosslinking agents can be used. Specific examples include organic peroxides, sulfur, sulfur compounds, and phenolic crosslinking agents.

[0066] Among these, organic peroxides are preferred because the resulting composition and its molded articles exhibit excellent transparency, high design quality, heat resistance, and mechanical properties. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0067] Among these, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis(tert-butylperoxy)valerate are preferred in terms of odor and scorch stability.

[0068] If the composition contains a crosslinking agent (E), the amount of crosslinking agent (E) in the composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8.0 parts by mass, even more preferably 0.1 to 5.0 parts by mass, and even more preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), from the viewpoint that a molded article with excellent hardness can be easily obtained.

[0069] <Other ingredients> ≪Crosslinking agent≫ When using the aforementioned crosslinking agent (E), it is preferable to use a crosslinking aid from the viewpoint of improving the efficiency of the crosslinking reaction.

[0070] There are no particular restrictions on the crosslinking aid; conventionally known crosslinking aids can be used, and they should be appropriately selected depending on the type of crosslinking agent (E). When an organic peroxide is used as the crosslinking agent (E), examples of the crosslinking aids include vinyl or methacrylate monomers such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N,4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, vinyl butyrate, vinyl stearate, elethin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate.

[0071] Among these, divinylbenzene is preferred because it has good compatibility with each component of this composition and also has a solubilizing effect on organic peroxides, thus acting as a dispersion aid for organic peroxides, which facilitates homogeneous crosslinking during heat treatment. Therefore, by using divinylbenzene as a crosslinking aid, it is possible to easily obtain this composition with a good balance of fluidity and physical properties.

[0072] If the composition contains a crosslinking aid, the amount of the crosslinking aid in the composition is preferably 0.01 to 10.0 parts by mass, more preferably 0.1 to 8.0 parts by mass, even more preferably 0.1 to 5.0 parts by mass, and particularly preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0073] <Other Polymerizations or Additives> This composition may, if necessary, contain other polymers or additives in addition to components (A) to (E), as long as it does not impair the purpose of the present invention.

[0074] Examples of other polymers include styrene-based thermoplastic elastomers, propylene-α-olefin random copolymers, butyl rubber, polyisobutylene rubber, nitrile rubber (NBR), natural rubber (NR), and silicone rubber.

[0075] When using other polymers, the amount added is usually 0.1 to 50 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). Each of the other polymers or additives may be used individually or in combination of two or more.

[0076] Examples of the styrene-based thermoplastic elastomers include styrene-isoprene block copolymers, hydrogenated styrene-isoprene block copolymers (SEP), hydrogenated styrene-isoprene-styrene block copolymers (SEPS; polystyrene-polyethylene / propylene-polystyrene block copolymer), styrene-butadiene copolymers (e.g., styrene-butadiene block copolymer), and hydrogenated styrene-butadiene block copolymers (SEBS; polystyrene-polyethylene / butylene-polystyrene block copolymer).

[0077] Other additives include crosslinking aids, antistatic agents, anti-aging agents, flame retardants, slip agents, nucleating agents, fillers, antioxidants, weather stabilizers, and colorants. When these other additives are used, their total amount is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of components (A) to (C). As for the filler, it is usually 1 to 50 parts by mass, preferably 1 to 45 parts by mass, and more preferably 1 to 40 parts by mass, based on 100 parts by mass of component (A).

[0078] Examples of the nucleating agents include non-melting and molten crystallization nucleating agents, which can be used individually or in combination of two or more. Examples of non-melting crystallization nucleating agents include inorganic substances such as talc, mica, silica, and aluminum, brominated biphenyl ethers, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), organophosphates, rosin-based crystallization nucleating agents, substituted triethylene glycol terephthalate, and terylene & nylon fibers. Particularly preferred are aluminum hydroxydi-p-tert-butylbenzoate, methylenebis(2,4-di-tert-butylphenyl) sodium phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl) sodium phosphate, and rosin-based crystallization nucleating agents.

[0079] Examples of sorbitol-based compounds that can be used as melt-type crystallization nucleating agents include dibenzylidene sorbitol (DBS), substituted DBS, and lower alkyl dibenzylidene sorbitol (PDTS).

[0080] Examples of the slip agent include fatty acid amides, silicone oils, glycerin, waxes, and paraffinic oils. Examples of the aforementioned fillers include conventionally known fillers, specifically one or more selected from carbon black, calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass spheres, shirasu balloons, basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, and the like.

[0081] <Method of manufacturing this composition and its physical properties> This composition can be produced by mixing and kneading an ethylene-α-olefin-non-conjugated polyene copolymer (A), a flexible propylene copolymer (B), a crystalline polyolefin (C), a softening agent (D), a crosslinking agent (E), and, if necessary, the aforementioned other additives.

[0082] The production of this composition can be carried out using common methods such as Banbury mixers, kneaders, single-screw extruders, and twin-screw extruders, which are commonly used in the production of ordinary resin compositions and elastomer compositions. Among these, twin-screw extruders are particularly preferred from the viewpoint of efficiently achieving dynamic crosslinking. Twin-screw extruders can not only uniformly and finely disperse components (A) to (E), but can also accelerate the crosslinking reaction by adding other components. As a result, the composition can be produced continuously, which is why they are preferred.

[0083] Furthermore, the present composition, in which at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked, is preferably produced by dynamically crosslinking (dynamically heat-treating) an uncrosslinked present composition, which is made by blending the ethylene-α-olefin-non-conjugated polyene copolymer (A), a flexible propylene copolymer (B), a crystalline polyolefin (C), a softening agent (D), a crosslinking agent (E), and, if necessary, the aforementioned other additives. The dynamic crosslinking can be performed, for example, by mixing and kneading components (A) to (E) and, if necessary, the aforementioned other polymers or additives, using a mixing and kneading device while heating, and it is preferable to crosslink while applying shear force. When performing dynamic crosslinking, it is preferable to use at least a crosslinking aid as the aforementioned other additive.

[0084] Furthermore, the flexible propylene copolymer (B) in this composition may be added either before or after dynamic crosslinking, or it may be added separately before and after dynamic crosslinking. By dynamic crosslinking, a composition can be obtained that contains a component in which at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked. Here, "at least a portion is crosslinked" means that the gel content is in the range of 5 to 98% by mass, preferably 10 to 95% by mass.

[0085] Dynamic crosslinking is preferably performed in a closed-type apparatus, and more preferably in an inert gas atmosphere such as nitrogen or carbon dioxide. The heating temperature in dynamic crosslinking is typically 125-280°C, preferably 145-240°C, and the mixing and kneading time is typically 1-30 minutes, preferably 3-20 minutes.

[0086] Furthermore, the shear force applied during the mixing and kneading process is such that the maximum shear rate is, for example, 10 to 100,000 seconds. -1 Preferably 100 to 50,000 seconds -1 , more comfortably 1,000~10,000 sec -1 More preferably 2,000 to 7,000 seconds -1 Examples of shear forces include the following.

[0087] Preferred embodiments of the method for producing this composition include, for example, the following. 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), Melting point (Tm B ) is not observed or the temperature is below 115°C, and the amount of soft propylene copolymer (B) is 0 to 5,000 parts by mass, preferably 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 4,000 parts by mass or less, 3,000 parts by mass or less, 2,500 parts by mass or less, Melting point (Tm C ) 10 to 500 parts by mass of crystalline polyolefin (C) whose temperature is 115°C or higher, Softener (D) 0 to 70 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and A first step involves dynamically crosslinking to obtain composition (i), The process includes a second step of adding 0 to 5,000 parts by mass, preferably 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 4,000 parts by mass or less, 3,000 parts by mass or less, and 2,500 parts by mass or less, to the above composition (i). The total amount of the soft propylene copolymer (B) added in the first and second steps is 20 to 5,000 parts by mass. A method for producing a thermoplastic elastomer composition wherein the soft propylene copolymer (B) further satisfies all of the following requirements (b-1) to (b-2): (b-1) Contains 90-50 mol% of propylene-derived constituent units, 0-30 mol% of 1-butene-derived constituent units, and 5-30 mol% of ethylene-derived constituent units. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5.

[0088] The first step described above involves introducing components (A) to (E) sequentially or simultaneously into a device capable of melting and kneading resin components, preferably a twin-screw extruder, and obtaining composition (i) by performing dynamic crosslinking under the conditions described above.

[0089] The second step described above is the step of adding a flexible propylene copolymer (B) to the composition (i) obtained in the first step. In the method for producing this composition, the second step may be carried out immediately following the first step, or the second step may be carried out after the first step, after the obtained composition (i) has been pelletized.

[0090] In the manufacturing method of the present invention, the flexible propylene copolymer (B) may be added in the first step only, in the second step only, or a portion may be added in the first step and the remainder in the second step. In the manufacturing method of the composition having a first step and a second step, it is preferable that the flexible propylene copolymer (B) is added in the second step only, that is, that the amount of the flexible propylene copolymer (B) added in the first step is 0 parts by mass. Furthermore, in the manufacturing method of the present invention, a portion or all of the softening agent constituting the composition may be added in the second step. When manufacturing the composition in a manner in which the flexible propylene copolymer (B) is added in the first step only, it is also preferable to manufacture the composition in a manner that does not have a second step, that is, in a manner that does not have a second step.

[0091] Furthermore, if this composition contains components other than components (A) to (E), these other components may be added in the first step or the second step. However, if a crosslinking aid is used, it is preferable to add the crosslinking aid in the first step.

[0092] The melt flow rate of this composition (according to the measurement method of JIS K 7210, at 230°C and a 10 kg load) is preferably 1 g / 10 min or more and less than 100 g / 10 min, and more preferably 1 g / 10 min or more and less than 80 g / 10 min, in order to obtain a composition with excellent moldability.

[0093] The Shore A hardness (instantaneous value) of this composition (according to the measurement method of JIS K 6253) is preferably 40 to 100, more preferably 50 to 95, and even more preferably 55 to 90.

[0094] When the Shore A hardness (instantaneous value) is within the aforementioned range, it is possible to obtain compositions and molded articles that have excellent design qualities such as tactile feel and a high-quality appearance, as well as scratch resistance necessary for practical use, and can be suitably used for parts such as automotive interior surface materials.

[0095] The Shore A hardness (instantaneous value) can be measured specifically by the method described in the examples below. This composition exhibits excellent moldability and can be suitably used in applications requiring aesthetic appeal, such as textured molding, and also boasts excellent transparency.

[0096] [Molded body] The molded article according to the present invention is not particularly limited as long as it includes the present composition, and is a molded article formed using any known molding method depending on the application. Examples of molding methods include press molding, injection molding, extrusion molding, calendering, hollow molding, vacuum molding, and compression molding. The molded article according to the present invention may be a molded article formed solely from the present composition, or it may be a molded article formed in combination with other materials. Furthermore, the molded article according to the present invention may be used alone or in combination with a molded article made of other materials.

[0097] The internal haze of the molded article according to the present invention is preferably 80% or less, more preferably 70% or less, and even more preferably 50% or less. When the internal haze is 80% or less, the transparency of the molded article is good. Here, the internal haze of the molded article refers to the haze excluding the haze caused by the shape of the outer surface of the molded article.

[0098] Furthermore, the total light transmittance of the molded article according to the present invention is preferably 83% or more, more preferably 85% or more. When the total light transmittance is 85% or more, the transparency of the molded article is good. Internal haze and total light transmittance can be measured specifically by the method described in the examples below.

[0099] The molded article according to the present invention is suitably used as an interior surface material for automobiles. Suitable examples of automotive interior upholstery materials include instrument panels, door trims, armrests, and consoles.

[0100] Furthermore, the molded body according to the present invention can be used as part of the interior finish of buildings (office buildings, hotels, shops, private homes, etc.). In addition, the molded body according to the present invention can be applied to a wide range of uses, including various display devices, decorative panels, LCD televisions, lighting switches, bathroom monitors, furniture, audio equipment, speakers, and home appliances (panels for rice cookers, microwave ovens, washing machines, air conditioners, telephones, remote controls, etc.).

[0101] <Decorative Panel> A molded article made from the thermoplastic elastomer composition of the present invention is suitable for use as a surface layer for a decorative panel equipped with a display device or an operating unit, because the composition exhibits excellent moldability and transparency. An example of a decorative panel according to the present invention is a decorative panel equipped with a display device or an operating unit.

[0102] The decorative panel of the present invention is 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (A), Melting point (Tm B ) is not observed or the temperature is below 115°C, 10 to 5,000 parts by mass of a soft propylene copolymer (B), Melting point (Tm C ) 10 to 500 parts by mass of crystalline polyolefin (C) whose temperature is 115°C or higher, Softener (D) 0 to 200 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and A molded article comprising a thermoplastic elastomer composition containing, A display device or operating unit provided at the lower part of the molded body, It is equipped with.

[0103] The thermoplastic elastomer composition included in the molded body constituting the decorative panel of the present invention is preferably the composition described above. Specifically, the preferred thermoplastic elastomer composition included in the molded body constituting the decorative panel of the present invention is 100 parts by mass of ethylene-α-olefin-nonconjugated polyene copolymer (A), Melting point (TmB ) is not observed or the temperature is below 115°C, and 20 to 5,000 parts by mass of a soft propylene copolymer (B), Melting point (Tm C ) 10 to 500 parts by mass of crystalline polyolefin (C) whose temperature is 115°C or higher, Softener (D) 0 to 70 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and Includes, The aforementioned flexible propylene copolymer (B) further satisfies the following requirement (b-1).

[0104] (b-1) Contains 90-50 mol% of propylene-derived constituent units, 0-30 mol% of 1-butene-derived constituent units, and 5-30 mol% of ethylene-derived constituent units. Preferably, the soft propylene copolymer (B) further satisfies the following requirement (b-2).

[0105] (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. The decorative panel of the present invention typically has a configuration in which a display device or operating unit is provided at the bottom of a molded body containing a thermoplastic elastomer composition, that is, a configuration in which a molded body containing a thermoplastic elastomer composition is provided on the display device or operating unit, and the display shown by the display device or operating unit can be viewed through the molded body containing the thermoplastic elastomer composition.

[0106] In one embodiment of the decorative panel of the present invention, when the light source of the display device or operating unit emits light, the display shown by the display device or operating unit can be viewed through the molded body containing the thermoplastic elastomer composition, while when the light source is not emitting light (non-emitting), only the surface of the molded body can be viewed.

[0107] Such decorative panels of the present invention can be suitably used in various devices equipped with instrument panels, display devices, or operating units in automobiles, and are particularly suitable for applications where aesthetic appeal is required, such as in the interior of an automobile or other interior space. [Examples]

[0108] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the following descriptions of examples, unless otherwise specified, "parts" refers to "parts by mass".

[0109] The methods for measuring the physical properties of the raw materials used in the examples and comparative examples are as follows. [Mass fraction of constituent units] The mass fraction (mass%) of each constituent unit contained in the ethylene-α-olefin-non-conjugated polyene copolymer (A-1) is: 13 The results were obtained from measurements using 1C-NMR. Specifically, using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.), the copolymer (A-1) was measured under the following conditions: measurement temperature: 120°C, measurement solvent: orthodichlorobenzene / deuterated benzene = 4 / 1 (volume ratio), and number of accumulation cycles: 8000. 13 It was calculated from the 1C-NMR spectrum.

[0110] [Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of flexible propylene copolymers (B-1), (B-2), and (B-3) were measured by gel permeation chromatography (GPC) at a column temperature of 140°C. Both the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured on a standard polystyrene basis. Mw / Mn was calculated based on the weight-average molecular weight (Mw) and number-average molecular weight (Mn).

[0111] [Melting point (Tm) and heat of fusion (ΔH)] The melting points of the soft propylene copolymers (B-1), (B-2), (B-3) and the crystalline polyolefins (C-1), (C-2) were determined by differential scanning calorimetry (DSC) using the following method.

[0112] 10 mg of the sample was placed in a dedicated aluminum pan and heated from room temperature to 200°C at a rate of 10°C / min using an X-DSC7000 (SII Corporation) under a nitrogen atmosphere. It was held at 200°C for 5 minutes, and then cooled to -100°C at a rate of 10°C / min. It was held at -100°C for 5 minutes, and then heated a second time to 200°C at a rate of 10°C / min. The melting point (Tm) and heat of fusion (ΔH) of the polymer were determined from the peak of the endothermic curve during the second heating.

[0113] The heat of fusion (ΔH) is calculated by using a line connecting a point on the low-temperature side where there is no change in heat quantity and a point on the high-temperature side where there is no change in heat quantity as a baseline, and determining the area enclosed by the line portion containing the peak of the endothermic curve obtained by the above measurement and the baseline.

[0114] In this case, if multiple peaks were detected in the endothermic curve, the temperature and peak area of ​​the peak detected at the highest temperature were defined as the melting point (Tm) and heat of fusion (ΔH), respectively. Furthermore, if no peak with a heat of fusion (ΔH) of 1 J / g or more was observed within the above measurement temperature range (-100°C to 200°C), it was assumed that neither the melting point (Tm) nor the heat of fusion (ΔH) was observed.

[0115] [Limiting viscosity] The intrinsic viscosity [η] of the aforementioned soft polypropylenes (B-1) and (B-2) was measured at 135°C using decalin solvent.

[0116] Specifically, approximately 20 mg of ethylene-α-olefin-non-conjugated polyene copolymer was dissolved in 15 ml of decalin, and the specific viscosity η was measured in an oil bath at 135°C. sp The specific viscosity η was measured. After diluting this decalin solution by adding 5 ml of decalin solvent, the specific viscosity η was measured in the same manner. sp The following was measured. This dilution procedure was repeated two more times, and the η obtained by extrapolating the concentration (C) to 0 was obtained. spThe value of / C was determined as the intrinsic viscosity (see the formula below). [η] = lim(ηsp / C) (C→0)

[0117] [Raw materials] The raw materials used in the examples and comparative examples are as follows:

[0118] (1) Ethylene-α-olefin-nonconjugated polyene copolymer (A-1) • Oil-expanded ethylene-propylene-non-conjugated diene copolymer rubber (EPDM, trade name: 3072EPM; manufactured by Mitsui Chemicals, Inc.) • Ethylene content = 64% by mass, Propylene content = 30.6% by mass, Non-conjugated diene species: 5-ethylidene-2-norbornene, Non-conjugated diene content = 5.4% by mass • Mooney viscosity [ML (1+4) 125℃ = 51 Oil spread (parts by mass) per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer = 40 (PHR) Note that the values ​​for copolymer (A-1) in Table 1 represent the amount of rubber components only, excluding the oil spreading amount. For spreading copolymer (A-1), paraffin-based process oil ("PW-100" manufactured by Idemitsu Kosan Co., Ltd., and the softener described below) was used.

[0119] (2) Flexible propylene copolymer (B) [Synthesis Example 1] Preparation of soft propylene copolymer (B-1) As a catalyst / co-catalyst, diphenylmethylene (3-t-butyl-5-ethylcyclopentadienyl)(2,7-t-fluorenyl) zirconium dichloride / methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., equivalent to 0.3 mmol of aluminum) prepared by the method described in Japanese Patent Publication No. 2007-186664 was used to polymerize the raw materials ethylene, propylene, and 1-butene in a hexane solution using a continuous polymerization apparatus to obtain propylene-1-butene-ethylene random copolymer (PBER-1) (76 mol% propylene, 6 mol% 1-butene, 18 mol% ethylene, melting point = not observed (ΔH = less than 0.5 J / g)), Mw / Mn = 2.1, intrinsic viscosity [η] = 1.4 dl / g).

[0120] [Synthesis Example 2] Preparation of soft propylene copolymer (B-2) As a catalyst / co-catalyst, diphenylmethylene (3-t-butyl-5-ethylcyclopentadienyl)(2,7-t-fluorenyl) zirconium dichloride / methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., equivalent to 0.3 mmol of aluminum) prepared by the method described in Japanese Patent Publication No. 2007-186664 was used to polymerize the raw materials ethylene, propylene, and 1-butene in a hexane solution using a continuous polymerization apparatus to obtain propylene-1-butene-ethylene random copolymer (PBER-1) (67 mol% propylene, 19 mol% 1-butene, 14 mol% ethylene, melting point = not observed (ΔH = less than 0.5 J / g), Mw / Mn = 2.1, intrinsic viscosity [η] = 1.8 dl / g).

[0121] Flexible propylene copolymer (B-3) • Propylene-α-olefin random copolymer (Trade name: Vistamaxx6102, manufactured by ExxonMobil, Ethylene content = 21.4 mol%, Melting point = 105°C, ΔH = 10 J / g, Mw / Mn = 2.1, MFR (230°C, 2.16 kg load) = 3.0 g / 10 min)

[0122] (3) Crystalline polyolefin (C) Crystalline polyolefin (C-1) • Propylene-ethylene block copolymer (product name: EL-Pro P740J; manufactured by SCG Chemicals, MFR (according to ASTM D 1238-65T measurement method; 230℃, 2.16kg load) = 27g / 10min), melting point = 163℃, ΔH = 93J / g) Crystalline polyolefin (C-2) • Propylene homopolymer (Trade name: Prime PolyPro J105; manufactured by Prime Polymer, Inc.; MFR (according to ASTM D 1238-65T measurement method; 230°C, 2.16 kg load) = 5 g / 10 min), melting point = 167°C, ΔH = 10⁵ J / g)

[0123] (4) Softener (D-1) • Paraffin-based process oil (Product name: Diana Process Oil PW-100, manufactured by Idemitsu Kosan Co., Ltd.) Note that the values ​​for the softener (D-1) in Table 1 include the amount derived from the oil spread of the copolymer.

[0124] (5) Crosslinking agent (E-1) • Organic peroxide (2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane), trade name: Perhexa 25B, manufactured by NOF Corporation) (6) Other ingredients (6-1) Crosslinking agent • Divinylbenzene (product name: DVB-810, manufactured by Nippon Steel Chemical & Material Co., Ltd.)

[0125] [Example 1] To 100 parts by mass of copolymer (A) (140 parts by mass of oil-expanded ethylene-propylene-non-conjugated diene copolymer rubber (EPDM, trade name: 3072EPM; manufactured by Mitsui Chemicals, Inc.), 2000 parts by mass of copolymer (B-1) synthesized in Synthesis Example 1, 350 parts by mass of crystalline polyolefin (C-1), 1.0 part by mass of crosslinking agent (E-1), and 1.0 part by mass of divinylbenzene as a crosslinking aid, the mixture was thoroughly mixed in a Henschel mixer. Granulation was performed using an extruder (model name: HYPERKTX-46, manufactured by Kobe Steel, Ltd., cylinder temperatures: C1=110℃, C2=120℃, C3=140℃, C4=140℃, C5=150℃, C6=160℃, C7~C8=180℃, C9~C14=230℃, die temperature: 200℃) while injecting a softening agent (D-1) into the cylinder so that the total amount including the oil spread of copolymer (A) was 50 parts by mass, thereby obtaining pellets of a thermoplastic elastomer composition.

[0126] [Example 2~ 3. Reference Examples 4-5, Examples 6-7 ] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1, except that the proportions of the raw materials used were changed as shown in Table 1.

[0127] [ reference Example 8] Except for changing the copolymer (B-1) used to copolymer (B-2) synthesized in Synthesis Example 2, and changing the proportions of the raw materials used as shown in Table 1, a thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1.

[0128] [ reference Example 9] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1, except that copolymer (B-1) used was changed to copolymer (B-3) and the proportions of the raw materials used were changed as shown in Table 1.

[0129] [ reference [Examples 10-11] Except for changing the proportions of the raw materials used as shown in Table 1 and using crystalline polyolefin (C-2), a thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1.

[0130] [Example 12] To 100 parts by mass of copolymer (A) (140 parts by mass of oil-expanded ethylene-propylene-non-conjugated diene copolymer rubber (EPDM, trade name: 3072EPM; manufactured by Mitsui Chemicals, Inc.), 350 parts by mass of crystalline polyolefin (C-1), 1.0 part by mass of crosslinking agent (E-1), and 1.0 part by mass of divinylbenzene as a crosslinking aid were thoroughly mixed in a Henschel mixer. Granulation was carried out using an extruder (model name: HYPERKTX-46, manufactured by Kobe Steel, Ltd., cylinder temperatures: C1=110℃, C2=120℃, C3=140℃, C4=140℃, C5=150℃, C6=160℃, C7~C8=180℃, C9~C14=230℃, die temperature: 200℃) while injecting a softener (D-1) into the cylinder so that the total amount including the oil spread of copolymer (A) was 50 parts by mass, thereby producing pellets of the thermoplastic elastomer composition. The obtained thermoplastic elastomer composition and 2000 parts by mass of copolymer (B-1) synthesized in Synthesis Example 1 were granulated again according to the above extrusion procedure to obtain pellets of the thermoplastic elastomer composition.

[0131] [ reference Example 13] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 12, except that the proportions of the raw materials used were changed as shown in Table 1.

[0132] [Comparative Examples 1-2] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1, except that copolymer (B-1) was not used and the proportions of the raw materials were changed as shown in Table 1.

[0133] [Method for evaluating thermoplastic elastomer compositions] <Preparation of press sheets> The pellets of the thermoplastic elastomer compositions obtained in the examples and comparative examples were press-formed using a hot press molding machine (press temperature: 190°C, cooling temperature: 20°C, preheating time: 6 minutes, pressurized melting time: 4 minutes). As a result of the press-forming, two types of flat press sheets with different thicknesses were produced for each composition. The resulting press sheets were 12 cm (length) x 14.7 cm (width) x 2 mm (thickness) and 12 cm (length) x 14.7 cm (width) x 0.5 mm (thickness), respectively.

[0134] <Shore A hardness (instantaneous value)> Three 2mm thick press sheets were stacked together and used as a test sample. The Shore A hardness (instantaneous value) was determined using a durometer in accordance with the method described in JIS K 6253. The results are shown in Table 1.

[0135] <Melt Flow Rate (MFR)> The melt flow rate was measured using pellets of the thermoplastic elastomer compositions obtained in the examples and comparative examples at 230°C and a 10 kg load, in accordance with JIS K 7210. The results are shown in Table 1.

[0136] <Modulus, stress at tensile fracture, elongation at tensile fracture> A dumbbell-shaped No. 3 test specimen was prepared by punching out the aforementioned 2 mm thick press sheet. Tensile tests were performed on the prepared test specimen in accordance with JIS K 6251 (tensile speed: 500 mm / min, measurement temperature: 23°C), and the modulus (M100), stress at break (TB), and elongation at break (EB) at 100% elongation were measured. The results are shown in Table 1.

[0137] <Internal haze, total light transmittance> Using the aforementioned 0.5 mm thick press sheet, the haze value and total light transmittance were measured in accordance with JIS K 7105. The results are shown in Table 1.

[0138] [Preparation of samples for evaluating vacuum formability (texture transferability, corner transferability)] Using the aforementioned thermoplastic elastomer composition pellets, a sheet with a thickness of 1.0 mm was produced using a T-die molding machine (manufactured by Toshiba Machine Co., Ltd., cylinder temperature: C1=160, C2=170, C3=180, C4=190, C5~C6=200℃, D1~D5=200℃, roll temperature: 60~80℃, take-up speed: 1.1 m / min, rotation speed: 55 rpm).

[0139] The aforementioned sheet was subjected to vacuum forming (forming temperature: 160°C, vacuum forming machine BVF-1010-PWB manufactured by Fuse Vacuum Co., Ltd.) to transfer the texture to a textured mold at the same time as forming the sheet, thereby producing molded samples of textured instrument panels and door trims. The texture transferability and corner transferability of the molded samples after forming were evaluated according to the following criteria.

[0140] <Texture transfer properties> The texture transfer properties were evaluated visually. A maximum score of 5 points was used, and the evaluation criteria were as follows. Three evaluators participated, and the score was determined by the average of their scores.

[0141] (Evaluation Criteria) 5 points: The texture of the molded product is transferred very clearly, demonstrating excellent texture transfer properties. 4 points: The texture of the molded product is clearly transferred, demonstrating excellent texture transfer properties. 3. The texture of the molded product is transferred to a recognizable degree, indicating good texture transferability. 2 points: The texture of the molded product is not fully transferred, indicating poor texture transfer performance. 1. The texture of the molded product is not transferred evenly, indicating poor texture transfer performance.

[0142] <Corner transferability> The transferability of the corner shape at the corner of the molded sample sheet was evaluated visually. The evaluation was based on a maximum score of 5 points, and the evaluation criteria were as follows. Three evaluators participated, and the score was determined by the average of the three evaluators' scores.

[0143] (Evaluation Criteria) 5 points: The corners of the molded part are transferred very clearly, and the corner transferability is excellent. 4 points: The corners of the molded product are clearly transferred, demonstrating excellent corner transferability. 3. The corners of the molded body are transferred to a recognizable degree, indicating good corner transferability. Points 2: The corners of the molded product are not transferred properly and are rounded, indicating poor corner transferability. 1 point: The corners of the molded part are not transferred properly and are rounded, indicating poor corner transferability.

[0144] [Table 1]

Claims

1. 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), Melting point (Tm B 210 to 5,000 parts by mass of a soft propylene copolymer (B) in which no ) is observed, Melting point (Tm C ) 30 to 500 parts by mass of crystalline polyolefin (C) having a temperature of 115°C or higher, Softener (D) 0 to 70 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and Includes, The aforementioned soft propylene copolymer (B) is a thermoplastic elastomer composition that further satisfies all of the following requirements (b-1) to (b-2): (b-1) Contains 90 to 50 mol% of propylene-derived constituent units, 1 to 30 mol% of 1-butene-derived constituent units, and 5 to 30 mol% of ethylene-derived constituent units. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.

5.

2. The thermoplastic elastomer composition according to claim 1, wherein the crosslinking agent (E) is an organic peroxide.

3. The thermoplastic elastomer composition according to claim 1 or 2, wherein the melt flow rate (measured according to the measurement method of JIS K 7210, at 230°C and a 10 kg load) is 1 g / 10 min or more and less than 80 g / 10 min.

4. The thermoplastic elastomer composition according to claim 1 or 2, wherein at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) is crosslinked.

5. The thermoplastic elastomer composition according to claim 1 or 2, wherein the Shore A hardness (instantaneous value) (measured according to the measurement method of JIS K 6253, using three sheets of 2 mm thickness stacked together) is 40 to 100.

6. A molded article comprising the thermoplastic elastomer composition according to claim 1 or 2.

7. The molded article according to claim 6, wherein the internal haze is 80% or less.

8. The molded article according to claim 6, wherein the total light transmittance is 83% or more.

9. The molded article according to claim 6, which is an automotive interior surface material.

10. The molded article according to claim 9, wherein the automotive interior surface material is an instrument panel, door trim, armrest, or console.

11. A molded article comprising the thermoplastic elastomer composition described in claim 1, A display device or operating unit provided at the lower part of the molded body, A decorative panel characterized by having the following features.

12. A method for producing a thermoplastic elastomer composition, wherein the production method is 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A), Melting point (Tm B ) 0 to 5,000 parts by mass of a soft propylene copolymer (B) in which no ) is observed, Melting point (Tm C ) 30 to 500 parts by mass of crystalline polyolefin (C) having a temperature of 115°C or higher, Softener (D) 0 to 70 parts by mass, Crosslinking agent (E) 0.01 to 10 parts by mass and A first step involves dynamically crosslinking to obtain composition (i), The process comprises a second step of adding 0 to 5,000 parts by mass of a soft propylene copolymer (B) to the composition (i), The total amount of the soft propylene copolymer (B) added in the first and second steps is 210 to 5,000 parts by mass. A method for producing a thermoplastic elastomer composition wherein the soft propylene copolymer (B) further satisfies all of the following requirements (b-1) to (b-2): (b-1) Contains 90 to 50 mol% of propylene-derived constituent units, 1 to 30 mol% of 1-butene-derived constituent units, and 5 to 30 mol% of ethylene-derived constituent units. (b-2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.

5.

13. A method for producing a thermoplastic elastomer composition according to claim 12, wherein the amount of the soft propylene copolymer (B) added in the first step is 0 parts by mass.

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