Thermoplastic elastomer composition and molded article thereof

Abstract

Provided are: a thermoplastic elastomer composition which exhibits excellent thermal aging resistance when exposed to a high-temperature environment for a long period of time, excellent hardness, excellent mechanical properties, and excellent extrusion processability; and the like. A thermoplastic elastomer composition (I) which contains a crosslinked product of an ethylene / alpha-olefin / non-conjugated polyene copolymer (A) having a weight average molecular weight of 350,000 or more and a phenolic resin-based crosslinking agent (E), and which contains 360-460 parts by mass of a crystalline polyolefin (B), 2-6 parts by mass of a fatty acid-based lubricant (D), and 80 parts by mass or more of a softening agent (C1) per 100 parts by mass of the copolymer (A), the 1 / 2 crystallization time of the thermoplastic elastomer composition (I) at 120 DEG C is 200 seconds or less, and the maximum spherocrystal size of the polyolefin component contained in the thermoplastic elastomer composition (I) is within the range of 8 [mu] m or less.

Description

Technical Field

[0001] The present invention relates to a thermoplastic elastomer composition and a molded product thereof. Background Art

[0002] As a molded body composed of a thermoplastic elastomer material containing a rubber component, a resin component, etc., a multilayer structure molded body is known in which a covering body having sliding properties is formed on the surface of a base body constituting the molded body (e.g., a portion requiring sliding properties). An example of such a multilayer structure molded body is a glass run channel for an automobile.

[0003] Materials for sliding covers used in automobile glass run channels are required to have various properties in a balanced manner, such as oil resistance, low oil penetration at high temperatures (hereinafter also referred to as "heat aging resistance"), hardness, mechanical strength, etc.

[0004] Regarding the heat aging resistance, there is the following idea: when the aforementioned covering body composed of a material containing a softener is stacked on the aforementioned substrate (glass run channel body) composed of a material containing a softener, due to the difference in the concentration of the softener in the covering body and the concentration of the softener in the substrate, the softener (oil) is transferred and oozing occurs.

[0005] Patent Document 1 discloses a thermoplastic elastomer composition comprising a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) (wherein the α-olefin has 3 to 20 carbon atoms) and a phenolic resin-based crosslinking agent (E), and further comprising 360 to 460 parts by mass of a crystalline polyolefin (B), 70 to 140 parts by mass of a softener (C), and 2 to 6 parts by mass of a fatty acid-based lubricant (D) relative to 100 parts by mass of the copolymer (A). The composition has excellent heat aging resistance, hardness and mechanical properties (tensile elastic modulus, tensile breaking strength), and excellent moldability.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2020 / 189633 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, it is known that the composition described in Patent Document 1 has room for further improvement in physical properties such as heat aging resistance.

[0011] An object of the present invention is to provide a thermoplastic elastomer composition having excellent heat aging resistance (specifically, heat aging resistance when exposed to a high temperature environment for a long period of time), excellent hardness and mechanical properties (tensile elastic modulus, tensile breaking strength), and excellent extrusion processability (specifically, the ability to suppress surface roughness of a molded article during extrusion molding), and a molded article using the same.

[0012] Means for solving problems

[0013] The present invention relates to, for example, the following [1] to

[13] . [1]

[0015] A thermoplastic elastomer composition (I) comprising a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) (wherein the α-olefin has 3 or more carbon atoms) satisfying the following requirements (a1) to (a4) and a phenolic resin crosslinking agent (E), and

[0016] The present invention comprises, relative to 100 parts by mass of the copolymer (A), 360 parts by mass to 460 parts by mass of a crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 minutes or less as measured at 230° C. and a load of 2.16 kg, 2 to 6 parts by mass of a fatty acid-based lubricant (D), and 80 parts by mass or more of a softener (C1),

[0017] The thermoplastic elastomer composition (I) has a 1 / 2 crystallization time of 200 seconds or less at 120°C, and a maximum spherulite size of a polyolefin component contained in the thermoplastic elastomer composition (I) is within a range of 8 μm or less.

[0018] (a1) The weight average molecular weight is 350,000 or more.

[0019] (a2) The intrinsic viscosity [η] is 4.0 dL / g or more.

[0020] (a3) The ethylene content is 57.0% by mass or more.

[0021] (a4) The non-conjugated polyene content is 4.0% by mass or more. [2]

[0023] The thermoplastic elastomer composition (I) according to [1], wherein the crystalline polyolefin (B) is a propylene homopolymer, and the melting point of the crystalline polyolefin (B) as measured by differential scanning calorimetry is 150 to 170°C. [3]

[0025] A molded article comprising the thermoplastic elastomer composition (I) according to [1] or [2]. [4]

[0027] A laminate comprising a layer comprising the thermoplastic elastomer composition (I) according to [1] or [2] and a layer comprising a soft material having a type A hardness of 50 to 95 as measured in accordance with ISO7619. [5]

[0029] The laminate according to [4], wherein the soft material has a type A hardness of 50 to 85. [6]

[0031] The laminate according to [4] or [5], wherein the soft material comprises a thermoplastic elastomer composition (II) containing a thermoplastic elastomer, the thermoplastic elastomer composition (II) comprises a softener (C2) having a solubility parameter of 6.6 to 7.1, and the mass fraction (W of the total amount of the softener (C2) relative to the thermoplastic elastomer composition (II) is 0.1:1. 2C ) is 30 to 60 mass %. [7]

[0033] The laminate according to any one of [4] to [6], wherein the mass fraction (W ) of the softener (C1) relative to the total mass fraction of the thermoplastic elastomer composition (I) is 1C ) and the aforementioned W 2C The ratio (W 1C / W 2C ) is less than 0.5. [8]

[0035] The molded article according to [3] is a window frame seal, a glass run channel, or a building material gasket. [9]

[0037] The laminate according to any one of [4] to [7], which is a window frame seal, a glass run channel, or a building material gasket.

[10]

[0039] A method for producing a thermoplastic elastomer composition (I), comprising the step (β) of mixing a mixture (α) comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfying the following requirements (a1) to (a4) (wherein the α-olefin has 3 or more carbon atoms) and a softener (C1), 360 to 460 parts by mass of a crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 min or less as measured at 230° C. and a load of 2.16 kg, 2 to 9 parts by mass of a phenolic resin crosslinking agent (E), 2 to 6 parts by mass of a fatty acid lubricant (D), and optionally a softener (C1) relative to 100 parts by mass of the copolymer (A);

[0040] The total amount of the softener (C1) contained in the aforementioned mixture (α) and the softener (C1) optionally mixed in the aforementioned step (β) is 80 parts by mass or more, and the mass fraction of the softener (C1) contained in the aforementioned mixture (α) relative to the total amount of the softener (C1) contained in the aforementioned mixture (α) and the softener (C1) optionally mixed in the aforementioned step (β) is 60 to 100% by mass.

[0041] (a1) The weight average molecular weight is 350,000 or more.

[0042] (a2) The intrinsic viscosity [η] is 4.0 dL / g or more.

[0043] (a3) The ethylene content is 57.0% by mass or more.

[0044] (a4) The non-conjugated polyene content is 4.0% by mass or more.

[11]

[0046] The method for producing a thermoplastic elastomer composition (I) according to

[10] , further comprising the step (α) of kneading the copolymer (A) and the softener (C1) to prepare the mixture (α).

[12]

[0048] The method for producing a thermoplastic elastomer composition (I) according to

[10] or

[11] , wherein the mass fraction of the softener (C1) contained in the mixture (α) relative to the total of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in the step (β) is 95% by mass to 100% by mass.

[13]

[0050] The method for producing a thermoplastic elastomer composition (I) according to any one of

[10] to

[12] , wherein the step (β) comprises a step of dynamically heat treating the copolymer (A), the crystalline polyolefin (B), the softener (C1) and the fatty acid lubricant (D) in the presence of the phenolic resin crosslinking agent (E).

[0051] Effects of the Invention

[0052] The thermoplastic elastomer composition of the present invention is excellent in heat aging resistance when exposed to a high temperature environment for a long period of time, is excellent in hardness and mechanical properties (tensile elastic modulus, tensile breaking strength), and is also excellent in extrusion processability.

[0053] Furthermore, the molded article and the laminate of the present invention are excellent in heat aging resistance when exposed to a high temperature environment for a long period of time, and are also excellent in hardness and mechanical properties (tensile elastic modulus, tensile breaking strength). BRIEF DESCRIPTION OF THE DRAWINGS

[0054] [ Figure 1 ] is an electron microscope photograph showing the spherulite state of the polyolefin component of the composition of Example 1.

[0055] [ Figure 2 ] is an electron microscope photograph showing the spherulite state of the polyolefin component of the composition of Comparative Example 5. DETAILED DESCRIPTION

[0056] [Thermoplastic elastomer composition (I)]

[0057] The thermoplastic elastomer composition (I) of the present invention is characterized in that it comprises a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfying the following requirements (a1) to (a4) and a phenolic resin-based crosslinking agent (E), and contains a crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 minutes or less measured under the conditions of 230° C. and a load of 2.16 kg, a softener (C1) and a fatty acid-based lubricant (D).

[0058] The thermoplastic elastomer composition (I) has a 1 / 2 crystallization time of 200 seconds or less at 120°C, and a maximum spherulite size of a polyolefin component contained in the thermoplastic elastomer composition (I) is within a range of 8 μm or less.

[0059] (a1) The weight average molecular weight is 350,000 or more.

[0060] (a2) The intrinsic viscosity [η] is 4.0 dL / g or more.

[0061] (a3) The ethylene content is 57.0% by mass or more.

[0062] (a4) The non-conjugated polyene content is 4.0% by mass or more.

[0063] <Ethylene-α-olefin-non-conjugated polyene copolymer (A)>

[0064] The ethylene-α-olefin-non-conjugated polyene copolymer (A) (hereinafter also referred to as "copolymer (A)") used in the present invention is an ethylene-α-olefin-non-conjugated polyene copolymer comprising a structural unit derived from ethylene, at least one structural unit derived from an α-olefin having 3 or more (preferably 20 or less) carbon atoms, and at least one structural unit derived from a non-conjugated polyene.

[0065] Examples of the α-olefins include: linear α-olefins without side chains, such as propylene (3 carbon atoms), 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-nonadecene (19 carbon atoms), and 1-eicosene (20 carbon atoms); and α-olefins with side chains, such as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These α-olefins may be used alone or in combination of two or more. Among them, α-olefins having 3 to 10 carbon atoms, such as propylene, 1-butene, 1-nonene, and 1-decene are preferred, and propylene is particularly preferred from the viewpoint of heat resistance.

[0066] Examples of the non-conjugated polyene include: chain non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene. Cyclic non-conjugated dienes such as cyclopentene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, etc. These non-conjugated polyenes may be used alone or in combination of two or more. Among them, cyclic non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and a mixture of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred, and 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are more preferred.

[0067] Examples of the copolymer (A) include ethylene-propylene-1,4-hexadiene copolymers, ethylene-1-pentene-1,4-hexadiene copolymers, ethylene-1-hexene-1,4-hexadiene copolymers, ethylene-1-heptene-1,4-hexadiene copolymers, ethylene-1-octene-1,4-hexadiene copolymers, ethylene-1-nonene-1,4-hexadiene copolymers, ethylene-1-decene-1,4-hexadiene copolymers, ethylene-propylene-1-octene-1,4-hexadiene copolymers, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene copolymer, ethylene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-1-nonene-5-ethylidene-2-norbornene copolymer, ethylene-1-decene-5-ethylidene-2-norbornene copolymers, ethylene-propylene-1-octene-5-ethylidene-2-norbornene copolymers, ethylene-propylene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymers, ethylene-1-pentene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymers, ethylene-1-hexene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymers, ethylene-1-heptene-5-ethylidene-2-norbornene-5-ethylidene ethylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-nonene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-decene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-propylene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, and the like.

[0068] The copolymer (A) may be used alone or in combination of two or more.

[0069] The copolymer (A) satisfies the following requirements (a1) to (a4).

[0070] (a1) The weight average molecular weight is 350,000 or more.

[0071] (a2) The intrinsic viscosity [η] is 4.0 dL / g or more.

[0072] (a3) The ethylene content is 57.0% by mass or more.

[0073] (a4) The non-conjugated polyene content is 4.0% by mass or more.

[0074] The lower limit of the weight average molecular weight (Mw) of the copolymer (A) is 350,000 or more, preferably 352,000 or more, and more preferably 355,000 or more. The upper limit of Mw is not particularly limited, but is usually 700,000 or less, and preferably 600,000 or less. These upper and lower limits may be combined arbitrarily.

[0075] A copolymer (A) having a Mw of less than 350,000 tends not to provide desired heat aging resistance.

[0076] The lower limit of the intrinsic viscosity [η] of the copolymer (A) measured in naphthalene at 135°C is 4.0 dL / g or more, preferably 4.1 dL / g or more, and more preferably 4.2 dL / g or more. The upper limit of the intrinsic viscosity [η] is not particularly limited, but is preferably 10.0 dL / g or less, and more preferably 8.0 dL / g or less. These upper and lower limits may be combined arbitrarily. When the intrinsic viscosity is less than 4.0 dL / g, there is a tendency that the desired heat aging resistance cannot be obtained.

[0077] The ethylene content of the copolymer (A) is 57.0% by mass or more, preferably 60.0 to 75.0% by mass, and more preferably 65.0 to 70.0% by mass.

[0078] The lower limit of the non-conjugated polyene content of the copolymer (A) is 4.0% by mass or more, preferably 4.2% by mass or more, and more preferably 4.4% by mass or more. The upper limit of the non-conjugated polyene content of the copolymer (A) can be set to 5.0% by mass or less. The upper and lower limits can be arbitrarily combined.

[0079] The ethylene content and non-conjugated polyene content of the copolymer (A) are determined by the following method: 13 The results were obtained by C-NMR method.

[0080] When the ethylene content of the copolymer (A) is less than 57.0% by mass, or the non-conjugated polyene content is less than 4.0% by mass, desired heat aging resistance tends to not be obtained.

[0081] The copolymer (A) may be composed only of monomers derived from fossil fuels, may be composed only of monomers derived from biomass, or may use a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0082] Fossil fuels refer to petroleum, coal, natural gas, shale gas or fuels made from a combination of these. Biomass refers to all renewable natural raw materials and their residues, including fungi, yeast, algae and bacteria, of plant or animal origin.

[0083] (Method for producing copolymer (A))

[0084] The copolymer (A) can be produced, for example, by the method described in

[0028] to

[0145] of International Publication No. 2018 / 181121.

[0085] <Crystalline Polyolefin (B)>

[0086] The crystalline polyolefin (B) is not particularly limited as long as it is a crystalline polymer obtained from an olefin, and is preferably a polymer formed from a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. Examples of such polymers include isotactic monoolefin polymers and syndiotactic monoolefin polymers.

[0087] The crystalline polyolefin (B) may be composed only of monomers derived from fossil fuels, may be composed only of monomers derived from biomass, or may use a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0088] The crystalline polyolefin (B) can be synthesized by a conventionally known method, or a commercially available product can be used.

[0089] The crystalline polyolefin (B) may be used alone or in combination of two or more.

[0090] Examples of olefins used as raw materials for the crystalline polyolefin (B) include α-olefins having 2 to 20 carbon atoms (excluding propylene), such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propylene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These may be used alone or in combination of two or more.

[0091] Among the crystalline polyolefins (B), propylene homopolymers or propylene copolymers obtained from olefins mainly containing propylene, i.e., propylene-based (co)polymers, are preferred from the perspective of heat resistance and oil resistance, and propylene homopolymers are more preferred from the perspective of tensile strength at break. In the case of propylene copolymers, the content of structural units derived from propylene is preferably 40 mol% or more, more preferably 50 mol% or more, and the olefin that becomes a structural unit derived from a monomer other than propylene is preferably an α-olefin having 2 to 20 carbon atoms (excluding propylene), and more preferably ethylene or butene.

[0092] The polymerization method may be random or block.

[0093] The melt flow rate (MFR) (ASTM D1238-65T, 230°C, 2.16 kg load) of the crystalline polyolefin (B) is usually 8.0 g / 10 minutes or less, preferably 0.05 to 5.0 g / 10 minutes, and more preferably 0.1 to 4.0 g / 10 minutes from the viewpoint of elastic modulus. When the MFR exceeds 8.0 g / 10 minutes, there is a tendency for poor moldability (extrusion processability).

[0094] The melting point (Tm) of the crystalline polyolefin (B) obtained by differential scanning calorimetry (DSC) is usually 100° C. or higher, preferably 105° C. or higher, and more preferably 150 to 170° C. When the melting point is within this range, the physical properties (hardness, mechanical properties, and moldability) suitable for the purpose of the present invention can be exhibited. The value of the melting point is the value when measured under the following conditions.

[0095] <Measurement Conditions>

[0096] About 5 mg of the sample is placed in a special aluminum pan, and a differential scanning calorimeter (e.g., DSC Pyris1 or DSC7 manufactured by PerkinElmer) is used to raise the temperature from 30°C to 200°C at 320°C / min, and after holding at 200°C for 5 minutes, the temperature is lowered from 200°C to 30°C at 10°C / min, and further held at 30°C for 5 minutes, and then the melting point is determined from the endothermic curve when the temperature is raised at 10°C / min. It should be noted that when multiple peaks are detected during DSC measurement, the peak temperature detected on the highest temperature side is defined as the melting point (Tm).

[0097] The crystalline polyolefin (B) plays a role in improving the fluidity and heat resistance of the thermoplastic elastomer composition.

[0098] The crystalline polyolefin (B) is usually used in an amount of 360 to 460 parts by mass, preferably 370 to 460 parts by mass, and more preferably 370 to 420 parts by mass, relative to 100 parts by mass of the copolymer (A). On the other hand, when the amount of the crystalline polyolefin (B) is too small compared to the above range, the hardness of the thermoplastic elastomer composition or its molded product is low, and when it is too large compared to the above range, the moldability (extrusion processability) of the thermoplastic elastomer composition is poor.

[0099] <Softener (C)>

[0100] As the softener (C), a softener generally used for rubber can be used. The softener (C) may be a non-biological oil, which is an oil obtained from a fossil raw material, or a biological oil, which is an oil obtained from an animal or plant raw material. Examples of the softener (C) include: petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; 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; factice; waxes such as beeswax, carnauba wax, and lanolin; fatty acids or fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and zinc laurate; cyclohexane acid; pine oil, rosin, or a derivative thereof; synthetic polymers such as terpene resins, petroleum resins, atactic polypropylene, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid mercaptan, and hydrocarbon-based synthetic lubricating oils. Among them, process oil and paraffin oil having a solubility parameter within a range of 6.1 to 7.1 are preferred.

[0101] Among them, petroleum-based softeners are preferred, and paraffin oil is particularly preferred.

[0102] The softener (C) (hereinafter referred to as softener (C1)) contained in the thermoplastic elastomer composition (I) is used in a proportion of usually 80 parts by mass or more, preferably 90 parts by mass or more, and usually 140 parts by mass or less, preferably 120 parts by mass or less, and more preferably 110 parts by mass or less, based on 100 parts by mass of the copolymer (A). The upper and lower limits may be combined arbitrarily.

[0103] When the softener (C1) is used in such an amount, the composition has excellent fluidity during preparation and molding, the mechanical properties of the obtained molded product are less likely to deteriorate, and the obtained molded product has excellent heat resistance and heat aging resistance.

[0104] <Fatty acid lubricant (D)>

[0105] As the fatty acid lubricant (D), a known fatty acid lubricant that is generally used in widely recognized plastics can be used. For example, the substances described in the 1037-1038 pages of the Chemical Handbook Applied Edition, Revised 2nd Edition (edited by the Chemical Society of Japan, 1973, published by Maruzen Co., Ltd.) can be used. As a specific example thereof, fatty acid amides can be mentioned.

[0106] Specific examples of the fatty acid amides include monoamides of higher fatty acids such as stearamide, hydroxystearamide, oleylamide, erucic acid amide (also known as erucic acid amide), lauramide, palmitamide, and behenamide;

[0107] Amides of higher fatty acids such as hydroxymethylamide, methylene bisstearamide, ethylene bisstearamide, ethylene bisoleamide and ethylene bislauramide;

[0108] Complex amides such as stearyl oleamide, N-stearoyl erucamide and N-oleyl palmitamide; and

[0109] Special fatty acid amides are commercially available as the trade names of Plastrodin and Plastrodin S (Fujisawa Pharmaceutical Industries, Ltd.).

[0110] These may be used alone or in combination of two or more.

[0111] Among them, monoamides of higher fatty acids are preferred, and erucamide is more preferred.

[0112] The fatty acid lubricant (D) is usually used in an amount of 2 to 6 parts by mass, preferably 3 to 5 parts by mass, relative to 100 parts by mass of the copolymer (A). When the fatty acid lubricant (D) is used in such an amount, the thermoplastic elastomer composition of the present invention has good mechanical properties and molding processability.

[0113] <Phenolic resin crosslinking agent (E)>

[0114] As the phenolic resin crosslinking agent (E) (also referred to as "crosslinking agent (E)" in the present invention), a resol phenolic resin produced by condensation of an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde, preferably with formaldehyde, in an alkaline medium, or produced by condensation of a difunctional phenol diol is also preferred. The alkyl-substituted phenol is preferably an alkyl-substituted product having 1 to 10 carbon atoms. Further preferred are dimethylolphenols or phenolic resins substituted at the para position with an alkyl group having 1 to 10 carbon atoms. The phenolic resin curing resin is typically a thermally crosslinkable resin, and is also referred to as a phenolic resin crosslinking agent or a phenolic resin. The crosslinking agent (E) generally plays a role in crosslinking the copolymer (A).

[0115] Examples of the phenolic resin-based curing resin (phenolic resin-based crosslinking agent) include resins represented by the following general formula [E1].

[0116] [Chemistry 1]

[0117]

[0118] (wherein, Q is a divalent group selected from the group consisting of -CH2- and -CH2-O-CH2-, m is 0 or a positive integer of 1 to 20, and R' is an organic group.

[0119] Preferably, Q is a divalent group -CH2-O-CH2-, m is 0 or a positive integer from 1 to 10, and R' is an organic group having less than 20 carbon atoms. More preferably, m is 0 or a positive integer from 1 to 5, and R' is an organic group having 4 to 12 carbon atoms.

[0120] Specifically, alkylphenol formaldehyde resins, methylolated alkylphenol resins, halogenated alkylphenol resins, etc. are mentioned, preferably halogenated alkylphenol resins, and more preferably those obtained by brominating the terminal hydroxyl group. Among the phenolic resin-based curing resins, one example of a terminally brominated resin is represented by the following general formula [E2].

[0121] [Chemistry 2]

[0122]

[0123] (In the formula, n is an integer of 0 to 10, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.)

[0124] Examples of the phenolic resin-based curing resin include Tackirol (registered trademark) 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Tackirol (registered trademark) 250-I (brominated alkylphenol formaldehyde resin with a bromination rate of 4%, manufactured by Taoka Chemical Industry Co., Ltd.), Tackirol (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (manufactured by Gunei Chemical Industry Co., Ltd.), Vulkaresat 510E (manufactured by Hoechst), Vulkaresat 532E (manufactured by Hoechst), Vulkaresen E (manufactured by Hoechst), Vulkaresen 105E (manufactured by Hoechst), Vulkaresen 130E (manufactured by Hoechst), Vulkaresol 315E (manufactured by Hoechst), Amberol ST137X (manufactured by Rohm & Haas), Sumilite Resin (registered trademark) PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphorm-C-100 (manufactured by Anchor Chem Co., Ltd.), Symphorm-C-1001 (manufactured by Anchor Chem Co., Ltd.), TAMANOL (registered trademark) 531 (manufactured by Arakawa Chemical Co., Ltd.), Schenectady SP1059 (manufactured by Schenectady Chem. Co., Ltd.), Schenectady SP1045 (manufactured by Schenectady Chem. Co., Ltd.), CRR-0803 (manufactured by UCC Co., Ltd.), Schenectady SP1055F (manufactured by Schenectady Chem. Co., Ltd., brominated alkylphenol formaldehyde resin), Schenectady SP1056 (manufactured by Schenectady Chem. Co., Ltd.), CRM-0803 (manufactured by Showa Union Synthesis Co., Ltd.), and Vulkadur A (manufactured by Bayer Co., Ltd.). Among them, a halogenated phenolic resin crosslinking agent is preferred, and a brominated alkylphenol formaldehyde resin such as Tackirol (registered trademark) 250-I, Tackirol (registered trademark) 250-III, or Schenectady SP1055F can be more preferably used.

[0125] Specific examples of crosslinking of thermoplastic vulcanizates with phenolic resins are described in US Pat. No. 4,311,628, US Pat. No. 2,972,600, and US Pat. No. 3,287,440, and these techniques can also be used in the present invention.

[0126] U.S. Patent No. 4,311,628 discloses a phenolic curative system consisting of a phenolic curing resin and a cure activator. The basic components of the system are condensation of substituted phenol (e.g., halogen-substituted phenol, C1-C2 alkyl-substituted phenol) or unsubstituted phenol with aldehyde, preferably formaldehyde, in an alkaline medium, or condensation of difunctional phenol diols (preferably with C5-C 10 A phenolic resin crosslinking agent produced by condensation of a phenolic resin crosslinking agent (alkyl-substituted dihydroxymethylphenols). A halogenated alkyl-substituted phenolic resin crosslinking agent produced by halogenation of an alkyl-substituted phenolic resin crosslinking agent is particularly suitable. A phenolic resin crosslinking agent composed of a hydroxymethylphenol curing resin, a halogen donor and a metal compound can be particularly recommended, and its details are described in the specifications of U.S. Patent No. 3,287,440 and U.S. Patent No. 3,709,840. A non-halogenated phenolic resin crosslinking agent is used together with a halogen donor, preferably together with a hydrogen halide scavenger. Generally, a halogenated phenolic resin crosslinking agent, preferably a brominated phenolic resin crosslinking agent containing 2 to 10% by mass of bromine, does not require a halogen donor, but is used together with a hydrogen halide scavenger such as a metal oxide such as iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and zinc oxide, preferably zinc oxide. These hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by mass relative to 100 parts by mass of the phenolic resin crosslinking agent. The presence of such a scavenger promotes the crosslinking action of the phenolic resin crosslinking agent, but in the case where the copolymer (A) is not easily crosslinked by the phenolic resin crosslinking agent (E), it is desirable to use a halogen donor and zinc oxide together. The preparation method of halogenated phenolic curable resins and their application in a vulcanizing agent system using zinc oxide are described in the specifications of U.S. Patent Nos. 2,972,600 and 3,093,613, and the disclosures thereof are incorporated into this specification as a reference together with the disclosures of the aforementioned U.S. Patent Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include halogen-donating polymers such as stannous chloride, ferric chloride, or chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and polychloroprene (chloroprene rubber). Suitable phenolic resin crosslinking agents and brominated phenolic resin crosslinking agents are commercially available, for example, the aforementioned crosslinking agents can be purchased from Schenectady Chemicals, Inc. under the trade names "SP-1045", "CRJ-352", "SP-1055F" and "SP-1056". Equivalent phenolic resin crosslinking agents having the same function can also be obtained from other suppliers.

[0127] The phenol resin crosslinking agent (E) generates little decomposition product and is therefore a suitable crosslinking agent from the viewpoint of preventing fogging.

[0128] In the present invention, when heat treatment is carried out in the presence of a crosslinking agent (E), auxiliary agents such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N,4-dinitroaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylenedimaleimide and the like, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate may be added.

[0129] In order to promote the decomposition of the crosslinking agent (E), a dispersion accelerator may be used. Examples of the decomposition accelerator include tertiary amines such as triethylamine, tributylamine, and 2,4,6-tris(dimethylamino)phenol; cyclopentane salts of aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury, and cyclopentane acids and various metals (e.g., Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, and rare earths); and the like.

[0130] The crosslinking agent (E) is usually used in an amount of 2 to 9 parts by mass, preferably 2.5 to 8.5 parts by mass, relative to 100 parts by mass of the copolymer (A). When the crosslinking agent (E) is used in such an amount, the thermoplastic elastomer composition of the present invention has good mechanical properties and molding processability. In addition, the degree of crosslinking of the copolymer (A) in the present invention is not particularly limited and can be adjusted by changing the amount of the crosslinking agent (E) within the scope of the present invention.

[0131] <Optional Additives>

[0132] The composition of the present invention may contain additives other than the above-mentioned components within a range that does not impair the effects of the present invention.

[0133] Examples of the additives include colorants, antioxidants, inorganic fillers, reinforcing agents, antioxidants (stabilizers), processing aids, activators, moisture absorbents, foaming agents, foaming aids, the above-mentioned crosslinking aids, the above-mentioned decomposition accelerators, and the like.

[0134] These additives may be used alone or in combination of two or more.

[0135] When optional additives are added, the amount of additives such as stabilizers (antioxidants, anti-aging agents) and processing aids is, for example, 0.01 to 0.80 parts by mass, preferably about 0.10 to 0.50 parts by mass, relative to 100 parts by mass of the copolymer (A). The amount of colorants, inorganic fillers, reinforcing agents, activators, hygroscopic agents, foaming agents, foaming aids, the above-mentioned crosslinking aids, the above-mentioned decomposition accelerators, etc. is not particularly limited, but when added, each additive is usually added in an amount of 0.01 to 10 parts by mass, preferably 1 to 8 parts by mass, relative to 100 parts by mass of the copolymer (A).

[0136] [Thermoplastic elastomer composition (I) and method for producing the same]

[0137] The thermoplastic elastomer composition (I) of the present invention contains the above-mentioned copolymer (A) crosslinked with a phenolic resin crosslinking agent (E), and contains:

[0138] 360 to 460 parts by mass of the crystalline polyolefin (B), 80 parts by mass or more of the softener (C1), and 2 to 6 parts by mass of the fatty acid lubricant (D) (wherein the amount of the copolymer (A) is 100 parts by mass).

[0139] The thermoplastic elastomer composition (I) of the present invention has a 1 / 2 crystallization time of 200 seconds or less, preferably 190 seconds or less, more preferably 180 seconds or less at 120°C, and its lower limit may be, for example, 60 seconds. In a composition having a 1 / 2 crystallization time of more than 200 seconds at 120°C, the crystalline polyolefin (B) in a molded article containing the composition is difficult to crystallize, and the softener permeation path in the molded article becomes larger. As a result, the softener retention is reduced, and the heat aging resistance is poor.

[0140] The 1 / 2 crystallization time is the time to reach 50% of the heat from the start of isothermal crystallization, when the area between the DSC heat curve and the baseline during isothermal crystallization is taken as the total heat. [Refer to New Polymer Experimental Lecture 8: Physical Properties of Polymers (Kyoritsu Publishing Co., Ltd.)] The 1 / 2 crystallization time is measured by the method using a differential scanning calorimeter (DSC) described later.

[0141] The 1 / 2 crystallization time of the composition (I) at 120°C can be adjusted by the components contained in the composition, for example, the type and amount of the crosslinking agent, whether the ethylene-α-olefin-non-conjugated polyene copolymer used as the raw material of the composition (I) is an oil-extended product, and the amount of oil-extended product when it is an oil-extended product, etc. In order to improve the heat aging resistance and extrusion processability of the composition (I), the ethylene-α-olefin-non-conjugated polyene copolymer (A) is preferably an oil-extended product, and the amount of oil-extended product is preferably 80 phr or more, more preferably 100 phr or more.

[0142] The maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) of the present invention is 8 μm or less, preferably 7 μm or less, and more preferably 6 μm or less. The maximum spherulite size can be set to, for example, 2 μm or more or 3 μm or more. In a composition in which the maximum spherulite size of the polyolefin component exceeds 8 μm, the molded body containing the composition becomes coarser and the softener penetration path in the molded body becomes larger. As a result, the retention of the softener decreases, resulting in poor heat aging resistance. In addition, due to the enlargement of the spherulites of the polyolefin component, unevenness is generated on the surface of the molded product, and the moldability, specifically, the extrusion processability is poor.

[0143] The minimum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) of the present invention is preferably in the range of 1 to 4 μm, more preferably 2 to 3 μm.

[0144] The maximum spherulite size and the minimum spherulite size of the polyolefin component of the composition (I) can be adjusted by the components contained in the composition, such as the type and amount of the ethylene-α-olefin-non-conjugated polyene copolymer, the amount of oil when it is an oil-extended product, the type and amount of the crystalline polyolefin, the type and amount of the crosslinking agent, the type and amount of the softener, the injection method, etc. More specifically, the softener injection method is controlled to disperse the softener in the ethylene-α-olefin-non-conjugated polyene copolymer and suppress the softener content in the crystalline polyolefin, thereby suppressing the crystallization hindrance of the crystalline polyolefin and controlling the spherulite size.

[0145] The value of the maximum spherulite size and the value of the minimum spherulite size are values ​​measured by the method used in the examples described later.

[0146] The thermoplastic elastomer composition (I) of the present invention can be obtained by a method comprising the following step (β).

[0147] Step (β): A mixture (α) comprising the copolymer (A) and the softener (C1) is mixed with 360 to 460 parts by mass of the crystalline polyolefin (B), 2 to 9 parts by mass of the phenolic resin crosslinking agent (E), 2 to 6 parts by mass of the fatty acid lubricant (D), and the softener (C1) as desired, relative to 100 parts by mass of the copolymer (A). The total amount of the softener (C1) contained in the mixture (α) and the softener (C1) as desired in the step (β) is 80 parts by mass or more.

[0148] The mass fraction of the softener (C1) contained in the mixture (α) relative to the total of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in the step (β) is usually 60 to 100 mass%, preferably 95 to 100 mass%. When the mass fraction is within this range, the 1 / 2 crystallization time at 120° C. of the thermoplastic elastomer composition (I) and the maximum spherulite size of the olefin component can be within the desired range, so that both heat aging resistance and extrusion processability can be achieved.

[0149] The mixture (α) may be the commercially available copolymer (A) oil-extended with the softener (C1).

[0150] Before the step (β), a step (α) of kneading the copolymer (A) and the softener (C1) to prepare the mixture (α) may be performed.

[0151] In the method for producing the thermoplastic elastomer composition (I) of the present invention, in a preferred embodiment, the step (β) includes a step of dynamically heat treating the copolymer (A), the crystalline polyolefin (B), the softener (C1) and the fatty acid lubricant (D) in the presence of the phenolic resin crosslinking agent (E).

[0152] The dynamic heat treatment is preferably carried out in a non-open device, and is preferably carried out in an inert gas atmosphere such as nitrogen or carbon dioxide. The heat treatment temperature is usually in the range of the melting point of the copolymer (A) to 300°C, preferably 150°C to 280°C, and more preferably 170°C to 270°C. The kneading time is usually 1 minute to 20 minutes, and preferably 1 minute to 10 minutes.

[0153] The dynamic heat treatment of the aforementioned mixture can be carried out using a known mixing device in the past. As the aforementioned mixing device, for example, a mixing roll, a strong mixer (such as a Banbury mixer, a pressure kneader), a single screw or a twin screw extruder can be enumerated, preferably a non-open type mixing device, particularly preferably a twin screw extruder.

[0154] Since the thermoplastic elastomer composition (I) of the present invention uses the copolymer (A) and the crosslinking agent (E) as raw materials, in a heat-treated product obtained by dynamically heat-treating the raw materials containing these, the copolymer (A) is usually crosslinked.

[0155] When producing the thermoplastic elastomer composition (I) of the present invention, the copolymer (A), the crosslinking agent (E) and at least a part of the crystalline polyolefin (B) may be dynamically heat-treated. The entire crystalline polyolefin (B) may be subjected to the dynamic heat-treatment. The softener (C1), the fatty acid-based lubricant (D) and the optional additives may be dynamically heat-treated together with at least a part of the copolymer (A), the crosslinking agent (E) and the crystalline polyolefin (B), respectively, or may be mixed with the heat-treated product, or may be both (i.e., a part may be dynamically heat-treated and the rest may be mixed with the heat-treated product).

[0156] The thermoplastic elastomer composition (I) of the present invention is preferably a composition containing paraffin oil as the softener (C1).

[0157] [Molded article and its use]

[0158] The molded article of the present invention is characterized by comprising the thermoplastic elastomer composition (I) of the present invention.

[0159] The molded article of the present invention can be formed from the thermoplastic elastomer composition (I) of the present invention. As a molding method, a conventionally known molding method can be applied.

[0160] The molded article of the present invention is excellent in sliding performance and processability.

[0161] The laminate of the present invention can be preferably used for articles such as window frame seals and building material gaskets in addition to glass run channels.

[0162] [Laminate and its use]

[0163] The laminate of the present invention is characterized by laminating a layer comprising the thermoplastic elastomer composition (I) of the present invention (ie, a layer serving as the molded product of the present invention) and a layer comprising a soft material.

[0164] Examples of the soft material include a soft material having a type A hardness of 50 to 95, and preferably 50 to 85. The type A hardness of the soft material is measured by a method in accordance with ISO7619 described below.

[0165] The soft material is not particularly limited as long as it has a type A hardness of 50 to 95, and examples thereof include thermoplastic elastomers (hereinafter also referred to as "thermoplastic elastomer composition (II)"). Commercially available products such as Milastomer C700BM, W600B, and TS7000N can be used as the soft material of the present invention.

[0166] Preferred examples of the thermoplastic elastomer composition (II) include the thermoplastic elastomer composition (I) of the present invention, a composition in which the phenolic resin crosslinking agent (E) in the thermoplastic elastomer composition (I) of the present invention is replaced with another crosslinking agent, and a composition in which the mixing ratio of the raw materials is changed in these thermoplastic elastomer compositions. As the thermoplastic elastomer composition (II), it is more preferred that the crosslinking agent is a phenolic resin crosslinking agent (E).

[0167] As the aforementioned thermoplastic elastomer composition (II), it is further preferred that the composition is produced by dynamically heat-treating 10 to 60 parts by mass of a polyolefin resin (X), 30 to 70 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer rubber (or a rubber component obtained by adding other rubbers such as polyisobutylene, butyl rubber, propylene-ethylene copolymer, etc.) (Y), and 5 to 50 parts by mass of an oily softener (Z) [the total of (X), (Y), and (Z) is 100 parts by mass.] in the presence of a crosslinking agent. Here, the components (X), (Y), and (Z) are respectively the same components as the components (B), (A), and (C) used in the thermoplastic elastomer composition (I) of the present invention.

[0168] The mass fraction (W) of the softener in the thermoplastic elastomer composition used in the present invention is c ) is defined as follows. That is, the value expressed as a percentage of the mass ratio of the softener (C) to the total mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A), the crystalline polyolefin (B), the softener (C) and the crosslinking agent (E') (the crosslinking agent (E') is a concept including the phenolic resin crosslinking agent (E)) in the thermoplastic elastomer composition used in the present invention is W. c Furthermore, W in the thermoplastic elastomer composition (I) c Represented as W 1c , W in the thermoplastic elastomer composition (II) c Represented as W 2c .

[0169] The aforementioned thermoplastic elastomer composition (II) contains a softener (C2) having a solubility parameter of 6.6 to 7.1.

[0170] The mass fraction (W) of the softener (C2) in the thermoplastic elastomer composition (II) is 2c ) is preferably 30 to 60 mass %, more preferably 33 to 55 mass %.

[0171] In the laminate, the mass fraction (W) of the softener (C1) relative to the total mass fraction (W) of the thermoplastic elastomer composition (I) is 1c) and the softener (C2) relative to the thermoplastic elastomer composition (II) in total (W 2c ) ratio (W 1c / W 2c ) is preferably 0.50 or less, more preferably 0.40 or less. 1c / W 2c ) is within the above range, the transfer of the softener (oil) from the layer containing the thermoplastic elastomer composition (I) to the layer containing the soft material (thermoplastic elastomer composition (II)) is small, and the sliding performance of the layer containing the thermoplastic elastomer composition (I) is not impaired. 1c / W 2c The lower limit of is not particularly limited, but is preferably 0.30, more preferably 0.40.

[0172] The laminate of the present invention may further have a layer other than the above two layers.

[0173] Although depending on the application of the laminate, the thickness of the layer containing the thermoplastic elastomer composition (I) is, for example, 30 to 1000 μm, and the thickness of the layer containing the soft material (thermoplastic elastomer composition (II)) is, for example, 0.1 to 3.0 mm.

[0174] The thermoplastic elastomer composition (I) of the present invention and its molded article are excellent in heat aging resistance, have appropriate hardness, and are also excellent in mechanical strength. Therefore, the laminate of the present invention using the thermoplastic elastomer composition (I) and its molded article is particularly useful for automobile sealing parts (glass run channels), and is considered to be able to reduce abnormal noise (rattle, squeak, rattling noise) when the bottom surface of the glass run channel strongly contacts the glass.

[0175] The laminate of the present invention can be preferably used for articles such as window frame seals and building material gaskets in addition to glass run channels.

[0176] Example

[0177] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[0178] [Measurement or evaluation method]

[0179] <Raw Materials>

[0180] The physical properties of the raw materials were measured by the following methods.

[0181] (Ratio of each structural unit in ethylene-α-olefin-non-conjugated polyene copolymer)

[0182] The ratio of the structural unit derived from ethylene, the ratio of the structural unit derived from α-olefin and the ratio of the structural unit derived from the non-conjugated polyene contained in the ethylene-α-olefin-non-conjugated polyene copolymer are determined by 13 The measurement was performed by C-NMR.

[0183] 13 The measurement conditions of C-NMR are as follows.

[0184] The measured values ​​were obtained by using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) at a temperature of 120°C, a solvent of o-dichlorobenzene / deuterated benzene = 4 / 1, and a cumulative number of 8000 times. 13 The results were obtained by C-NMR spectrum.

[0185] (Number average molecular weight and weight average molecular weight)

[0186] The number average molecular weight and weight average molecular weight of the ethylene-α-olefin-non-conjugated polyene copolymer are measured by gel permeation chromatography under the following conditions.

[0187] Column: TSKgel GMH6-HT×2+TSKgel GMH6-HTL×2

[0188] (All 7.5mm I.D.×30cm, manufactured by Tosoh Corporation)

[0189] Column temperature: 140°C

[0190] Mobile phase: o-dichlorobenzene (containing 0.025% BHT)

[0191] Detector: Differential Refractometer

[0192] Flow rate: 1.0mL / min

[0193] Sample concentration: 0.1% (w / v)

[0194] Injection volume: 0.4mL

[0195] Sampling time interval: 0.5 seconds

[0196] Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation); #3std set

[0197] Molecular weight conversion: PS conversion / standard product conversion method

[0198] (Intrinsic viscosity [η])

[0199] The intrinsic viscosity [η] of the ethylene-α-olefin-non-conjugated polyene copolymer was measured using a fully automatic intrinsic viscosity meter manufactured by Rigo Co., Ltd. at a temperature of 135° C. and a measurement solvent of decalin.

[0200] (Solubility Parameter)

[0201] The solubility parameters of the softener were calculated using the parameters of Fedors using the Synthia module of Materials Studio.

[0202] <Thermoplastic Elastomer Composition>

[0203] The thermoplastic elastomer composition was measured or evaluated by the following method.

[0204] (MFR)

[0205] The melt flow rate (MFR) of the pellets of the thermoplastic elastomer composition at 230° C. and a load of 10 kg was measured using a Melt Indexer (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with JIS K7112.

[0206] (Type A hardness)

[0207] The soft material was pressed at 230°C for 6 minutes using a 100t electric heating automatic press (manufactured by Shoji Co.), and then cooled and pressed at room temperature for 5 minutes to produce a pressed sheet with a thickness of 2 mm. The sheet was used in accordance with ISO7619, using an A-type measuring instrument, and the scale was read immediately after the pressure needle contacted. When the measured A-type hardness was 50 to 95, the soft material was the soft material of the present invention.

[0208] (D-type hardness)

[0209] A sheet sample of 20 cm×20 cm×2 mm prepared from pellets of the thermoplastic elastomer composition using a 50 t press was used as a test sample, and the hardness was measured using a durometer type D durometer in accordance with JIS K 6252-3.

[0210] (Tensile properties)

[0211] A sheet sample of 20 cm × 20 cm × 2 mm prepared from pellets of the thermoplastic elastomer composition using a 50 t press was used as a test sample. A tensile test was carried out in accordance with JIS 6251 at a temperature of 25°C and a tensile speed of 500 mm / min to measure M100 (stress at 100% elongation), TB (tensile breaking strength) and EB (tensile breaking elongation).

[0212] (1 / 2 crystallization time)

[0213] The pellets of the thermoplastic elastomer composition were heated to 230°C at a heating rate of 500°C / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC), maintained for 10 minutes, and then cooled to 120°C at a cooling rate of 500°C / min to measure the 1 / 2 crystallization time.

[0214] (Maximum spherulite size and minimum spherulite size)

[0215] The polyolefin component in the laminate produced in the examples and the like is dyed with RuO4, and carbon vapor deposition is performed on a thin sheet cut in the TD direction. Five randomly selected locations in the laminate are observed with a transmission microscope (TEM) at a magnification of 10,000 times, and the diameters of the largest and smallest spherulites of the polyolefin component within the observation range are measured. The respective average values ​​are taken as the maximum spherulite size and the minimum spherulite size. In addition, the portion surrounded by the boundary line of the white portion (crystalline resin component) not dyed by the dye is defined as one spherulite. It should be noted that in the case where the spherulites are not circular (i.e., elliptical or polygonal), the cut surface (i.e., Figure 1 and Figure 2 ) in the horizontal or vertical direction as the maximum and minimum values ​​are taken as the maximum spherulite size and the minimum spherulite size.

[0216] (Heat aging resistance)

[0217] The laminates prepared in the examples were placed in air at 85°C for 168 hours, and the surface condition of the sliding layer (thermoplastic elastomer composition (I)) side of the laminate was confirmed by visual inspection and touch, and compared with the surface condition before placement. The meanings of the symbols in Tables 2 and 3 are as follows.

[0218] 0: No change in surface condition

[0219] △: The surface is glossy but not sticky

[0220] ×: The surface is glossy and sticky

[0221] (Extrusion Processability)

[0222] The extrusion processability of the thermoplastic elastomer composition was evaluated visually by the appearance when laminated and extruded together with the soft material. The composition without any problem was evaluated as good, and the composition with abnormality such as surface roughness was evaluated as poor.

[0223] [raw material]

[0224] As the ethylene-α-olefin-non-conjugated polyene copolymer, the following ethylene-propylene-diene copolymer (hereinafter referred to as "EPDM") was used.

[0225] EPDM-1 Trade name: Mitsui EPT (trademark) X-3042E (Made by Mitsui Chemicals, Inc.)

[0226] EPDM-2 (trademark) KEP902 NP (manufactured by KUMHO POLYCHME Co., Ltd.)

[0227] EPDM-3 Trade name: Mitsui EPT (trademark) 3072EPM (Made by Mitsui Chemicals, Inc.)

[0228] EPDM-4 Trade name: Mitsui EPT (trademark) 4100E (Made by Mitsui Chemicals, Inc.)

[0229] Table 1 shows the physical properties of EPDM contained in the above EPDM-1 to EPDM-4.

[0230] EPDM-1 to EPDM-4 are so-called oil-extended products in which a softener is blended into EPDM. In Table 1, the content of the softener relative to 100 parts by mass of EPDM is described as "amount of oil extension".

[0231] [Table 1]

[0232] EPDM-1 EPDM-2 EPDM-3 EPDM-4 EPDM Properties Ethylene content quality% 67.0 67.0 64.0 57.0 Diene content quality% 4.3 4.5 5.4 7.3 Number average molecular weight - 131,000 238,000 115,000 140,000 Weight average molecular weight - 353,000 638,000 284,000 471，000 Intrinsic viscosity [η] dL / g 4.3 5.0 3.4 4.1 Oil filling amount Mass 120 100 40 50

[0233] As the crystalline polyolefin (B), the following propylene homopolymers PP-1 to PP-3 produced by a known technique were used.

[0234] PP-1: propylene homopolymer with MFR (230°C, 2.16 kg load) = 0.5 g / 10 min, melting point 160°C

[0235] PP-2: propylene homopolymer with MFR (230°C, 2.16 kg load) = 2.0 g / 10 min, melting point 160°C

[0236] PP-3: propylene homopolymer with MFR (230°C, 2.16 kg load) = 9.0 g / 10 min, melting point 160°C

[0237] Furthermore, the following raw materials were used.

[0238] Softener: PW90 (trade name, manufactured by Idemitsu Kosan Co., Ltd.) (paraffin oil)

[0239] Lubricant: Erucic acid amide

[0240] · Cross-linking agent: Brominated alkylphenol formaldehyde resin (trade name, SP-1055F, manufactured by Schenectady)

[0241] Colorant: Carbon black masterbatch (DIC Corporation, F23287MM)

[0242] Antioxidant: A mixture of a phenolic antioxidant (Irganox 1010 (manufactured by BASF Japan)), a benzotriazole ultraviolet absorber (Tinuvin 326 (manufactured by BASF Japan)), and a hindered amine (HALS) weathering stabilizer (Tinuvin 770 (manufactured by BASF Japan)

[0243] [Example 1]

[0244] (Production of Thermoplastic Elastomer Composition-1)

[0245] EPDM-1, PP-1, a softener, a lubricant, a crosslinking agent, a colorant and an antioxidant were introduced into a twin-screw extruder (HYPER KTX 46 manufactured by Kobe Steel) at the ratios shown in Table 2, and melt-kneaded under the conditions of a barrel temperature of 50°C to 250°C (i.e., the temperature of the dynamic heat treatment described in the above-mentioned "Thermoplastic elastomer composition (I) and its production method" is 250°C), a die temperature of 200°C, a screw speed of 550 pm, and an extrusion rate of 40 kg / hour to obtain pellets of a thermoplastic elastomer composition (hereinafter also referred to as "thermoplastic elastomer composition-1"). The evaluation results are shown in Table 2.

[0246] (Manufacturing of Laminated Body)

[0247] As the material of the layer containing the soft material (thermoplastic elastomer composition (II)), a softener (C2) having a mass fraction (W 2c ) is a thermoplastic elastomer composition with 42 mass % (TPV-1, type A hardness 70) or 50 mass % (TPV-2, type A hardness 70).

[0248] Specifically, 24 parts by mass of a polyolefin resin (the aforementioned PP-1), 37 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer (the aforementioned EPDM-1), and 33 parts by mass of a softener (C2) (solubility parameter = 7.1) were dynamically heat-treated in the presence of 6 parts by mass of a crosslinking agent (the aforementioned brominated alkylphenol formaldehyde resin) under the same conditions as in the production of the aforementioned thermoplastic elastomer composition-1, thereby producing a thermoplastic elastomer composition (hereinafter referred to as "TPV-1"). Separately, 19 parts by mass of a polyolefin resin (the aforementioned PP1), 33 parts by mass of an ethylene-α-olefin-non-conjugated polyene copolymer (the aforementioned EPDM-1), and 42 parts by mass of a softener (C2) (solubility parameter = 7.1) were dynamically heat-treated in the presence of 6 parts by mass of a crosslinking agent (the aforementioned brominated alkylphenol formaldehyde resin) under the same conditions as in the production of the aforementioned thermoplastic elastomer composition-1, thereby producing a thermoplastic elastomer composition (hereinafter referred to as "TPV-2").

[0249] A coextrusion device was used to prepare a laminate (sliding layer thickness 200 to 250 μm, laminate total thickness 2 mm) comprising a layer containing a soft material (TPV-1 or TPV-2) and a sliding layer containing thermoplastic elastomer composition-1.

[0250] Table 2 shows the evaluation results of the heat aging resistance of the laminate as a test sample.

[0251] [Examples 2 to 8, Comparative Examples 1 to 6]

[0252] Pellets of a thermoplastic elastomer composition were obtained and a laminate was produced in the same manner as in Example 1 except that the types and amounts of the raw materials were changed as shown in Table 1. The evaluation results are shown in Tables 2 and 3.

[0253] [Table 2]

[0254]

[0255] [Table 3]

[0256]

Claims

1. A thermoplastic elastomer composition (I), comprising a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfying the following requirements (a1) to (a4) and a phenolic resin crosslinking agent (E), wherein the α-olefin in the copolymer (A) has 3 or more carbon atoms, and The present invention comprises, with respect to 100 parts by mass of the copolymer (A), 360 parts by mass to 460 parts by mass of a crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 minutes or less as measured at 230° C. and a load of 2.16 kg, 2 parts by mass to 6 parts by mass of a fatty acid-based lubricant (D), and 80 parts by mass or more of a softener (C1), The thermoplastic elastomer composition (I) has a 1 / 2 crystallization time of 200 seconds or less at 120°C. The maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) is within the range of 8 μm or less, (a1) a weight average molecular weight of 350,000 or more, (a2) the intrinsic viscosity η is 4.0 dL / g or more, (a3) an ethylene content of 57.0% by mass or more, (a4) The non-conjugated polyene content is 4.0% by mass or more.

2. The thermoplastic elastomer composition (I) according to claim 1, wherein The crystalline polyolefin (B) is a propylene homopolymer, and the melting point of the crystalline polyolefin (B) measured by differential scanning calorimetry is 150 to 170°C.

3. A molded article comprising the thermoplastic elastomer composition (I) according to claim 1 or 2.

4. A laminate comprising a layer comprising the thermoplastic elastomer composition (I) according to claim 1 or 2 and a layer comprising a soft material having a type A hardness of 50 to 95 as measured in accordance with ISO7619.

5. The laminate according to claim 4, wherein The soft material has a type A hardness of 50-85.

6. The laminate according to claim 4, wherein The soft material comprises a thermoplastic elastomer composition (II) containing a thermoplastic elastomer, The thermoplastic elastomer composition (II) comprises a softener (C2) having a solubility parameter of 6.6 to 7.1, The total mass fraction of the softener (C2) relative to the thermoplastic elastomer composition (II) is W 2C It is 30 to 60% by mass.

7. The laminate according to claim 6, wherein: The total mass fraction of the softener (C1) relative to the thermoplastic elastomer composition (I), i.e., W 1C With the W 2C The ratio of W 1C / W 2C Is below 0.

5.

8. The molded article according to claim 3, which is a window frame seal, a glass run channel or a building material gasket. 9 . The laminate according to claim 4 , which is a window frame seal, a glass run channel, or a building material gasket.

10. A method for producing a thermoplastic elastomer composition (I), comprising the step (β) of mixing a mixture (α) comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfying the following requirements (a1) to (a4) and a softener (C1), 360 to 460 parts by mass of a crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 min or less as measured at 230° C. and a load of 2.16 kg, 2 to 9 parts by mass of a phenolic resin crosslinking agent (E), 2 to 6 parts by mass of a fatty acid lubricant (D), and optionally a softener (C1) relative to 100 parts by mass of the copolymer (A), wherein the α-olefin in the copolymer (A) has 3 or more carbon atoms, The total amount of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in the step (β) is 80 parts by mass or more, The mass fraction of the softener (C1) contained in the mixture (α) relative to the total of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in the step (β) is 60 to 100 mass%, (a1) a weight average molecular weight of 350,000 or more, (a2) the intrinsic viscosity η is 4.0 dL / g or more, (a3) an ethylene content of 57.0% by mass or more, (a4) The non-conjugated polyene content is 4.0% by mass or more. 11 . The method for producing a thermoplastic elastomer composition (I) according to claim 10 , further comprising a step (α) of kneading the copolymer (A) and the softener (C1) to prepare the mixture (α).

12. The method for producing a thermoplastic elastomer composition (I) according to claim 10 or 11, wherein: The mass fraction of the softener (C1) contained in the mixture (α) relative to the total of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in the step (β) is 95% by mass to 100% by mass.

13. The method for producing a thermoplastic elastomer composition (I) according to claim 10 or 11, wherein: The step (β) includes a step of dynamically heat treating the copolymer (A), the crystalline polyolefin (B), the softener (C1) and the fatty acid lubricant (D) in the presence of the phenolic resin crosslinking agent (E).

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