Thermoplastic elastomer composition and molded article thereof

Abstract

Provided is a thermoplastic elastomer composition, etc. that has excellent thermal aging resistance during long-term exposure to a high-temperature environment, excellent hardness and mechanical properties, and excellent extrusion processability.　The thermoplastic elastomer composition (I) contains a crosslinked product of an α-olefin-unconjugated polyene copolymer (A) having a weight average molecular weight of 350,000 or more and a phenolic resin crosslinking agent (E), and contains 360 mass parts to 460 mass parts of a crystalline polyolefin (B), 2 to 6 mass parts of a fatty acid lubricant (D), and 80 mass parts or more of a softening agent (C1) per 100 mass parts of the copolymer (A); the ½ crystallization time of the thermoplastic elastomer composition (I) at 120°C is 200 seconds or less, and the maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) is in the range of 8 μm or less.

Description

[Technical Field]

[0001] This invention relates to a thermoplastic elastomer composition and a molded article thereof. [Background technology]

[0002] As molded articles made of thermoplastic elastomer materials containing rubber components, resin components, etc., a multilayer structure is known in which a sliding coating is formed on the surface of the substrate constituting the molded article (for example, in a part requiring sliding properties). An example of such a multilayer molded article is the glass run channel in an automobile.

[0003] Materials used for sliding coatings in automotive glass run channels are required to possess a good balance of various properties. These properties include, in particular, oil resistance, low oil bleeding at high temperatures (hereinafter also referred to as "heat aging resistance"), hardness, and mechanical strength.

[0004] Regarding this heat aging resistance, one theory is that when the coating, which is made of a material containing a softening agent, is laminated onto the substrate (glass run channel body), which is made of a material containing a softening agent, the difference in concentration of the softening agent in the coating and the substrate causes the softening agent (oil) to migrate, resulting in a bleeding phenomenon.

[0005] Patent Document 1 discloses a thermoplastic elastomer composition that contains a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) (where the number of carbon atoms in the α-olefin is 3 to 20) with a phenolic resin-based crosslinking agent (E), and further contains 360 to 460 parts by mass of 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) per 100 parts by mass of the copolymer (A), thereby exhibiting excellent heat aging resistance, excellent hardness and mechanical properties (tensile modulus, tensile breaking strength), and excellent moldability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2020 / 189633 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, it was found that the composition described in Patent Document 1 has room for further improvement in physical properties such as heat aging resistance.

[0008] The present invention aims to provide a thermoplastic elastomer composition that exhibits excellent heat aging resistance (specifically, heat aging resistance when exposed to high-temperature environments for extended periods), excellent hardness and mechanical properties (tensile modulus, tensile breaking strength), and excellent extrusion processability (specifically, it can suppress surface roughness of molded products during extrusion molding), and molded articles using the same. [Means for solving the problem]

[0009] The present invention relates, for example, to the following [1] to

[13] . [1] The product includes a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) (where the α-olefin has 3 or more carbon atoms) that satisfies the following requirements (a1) to (a4) and a phenolic resin-based crosslinking agent (E), and Amount to 100 parts by mass of the copolymer (A): 360 to 460 parts by mass of crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 min or less as measured under conditions of 230°C and a 2.16 kg load, Fatty acid-based lubricant (D) in 2 to 6 parts by mass, and A thermoplastic elastomer composition (I) containing 80 parts by mass or more of a softening agent (C1), The half-crystallization time of the thermoplastic elastomer composition (I) at 120°C is 200 seconds or less. The thermoplastic elastomer composition (I) in which the maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) is in the range of 8 μm or less. (a1) The weight average molecular weight is 350,000 or more. (a2) The intrinsic viscosity [η] is 4.0 dL / g or more. (a3) The ethylene content is 57.0 mass% or more. (a4) The non-conjugated polyene content is 4.0 mass% or more.

[0010] [2] The thermoplastic elastomer composition (I) according to [1], wherein the crystalline polyolefin (B) is a propylene homopolymer and the melting point measured by differential scanning calorimetry of the crystalline polyolefin (B) is 150 to 170 °C.

[0011] [3] A molded article containing the thermoplastic elastomer composition (I) according to [1] or [2].

[0012] [4] A layer containing the thermoplastic elastomer composition (I) according to [1] or [2], and a layer containing a soft material having a type A hardness of 50 to 95 measured in accordance with ISO 7619, laminated together.

[0013] [5] The laminate according to [4], wherein the type A hardness of the soft material is 50 to 85.

[0014] [6] The soft material contains a thermoplastic elastomer composition (II) containing a thermoplastic elastomer, the thermoplastic elastomer composition (II) contains a softening agent (C2) having a solubility parameter of 6.6 to 7.1, and the mass fraction (W 2C ) of the softening agent (C2) with respect to the total of the thermoplastic elastomer composition (II) is 30 to 60 mass%. The laminate according to [4] or [5].

[0015] [7] The mass fraction (W) of the softener (C1) relative to the total amount of the thermoplastic elastomer composition (I) 1C ) of the aforementioned W 2C Ratio to (W 1C / W 2C A laminate according to any of [4] to [6], wherein ) is 0.5 or less.

[0016] [8] The molded body described in [3] is a window frame seal, a glass run channel, or a building material gasket.

[0017] [9] A laminate as described in any of [4] to [7], which is a window frame seal, a glass run channel, or a building material gasket.

[0018]

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

[11] A 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).

[0019]

[12] A 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) and the softener (C1) optionally mixed in the step (β) is 95 to 100% by mass.

[0020]

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

[10] to

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

[0021] The thermoplastic elastomer composition of the present invention exhibits excellent heat aging resistance when exposed to high-temperature environments for extended periods, as well as excellent hardness and mechanical properties (tensile modulus, tensile strength), and also has excellent extrusion processability. Furthermore, the molded articles and laminates of the present invention exhibit excellent heat aging resistance when exposed to high-temperature environments for extended periods, and also possess excellent hardness and mechanical properties (tensile modulus, tensile fracture strength). [Brief explanation of the drawing]

[0022] [Figure 1] Electron microscope image showing the spherulitic state of the polyolefin component of the composition of Example 1. [Figure 2]Electron microscope image showing the spherulitic state of the polyolefin component in the composition of Comparative Example 5. [Modes for carrying out the invention]

[0023] [Thermoplastic elastomer composition (I)] The thermoplastic elastomer composition (I) according to the present invention is The product comprises a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) that satisfies the following requirements (a1) to (a4), and a phenolic resin-based crosslinking agent (E), and It contains crystalline polyolefin (B), a softener (C1), and a fatty acid-based lubricant (D), with a melt flow rate of 8.0 g / 10 min or less as measured under conditions of 230°C and a 2.16 kg load. The half-crystallization time of the thermoplastic elastomer composition (I) at 120°C is 200 seconds or less. The thermoplastic elastomer composition (I) is characterized in that the maximum spherulite size of the polyolefin component contained in it is in the range of 8 μm or less. (a1) The weight-average molecular weight is 350,000 or more. (a2) The intrinsic viscosity [η] is 4.0 dL / g or greater. (a3) The ethylene content is 57.0% by mass or more. (a4) The non-conjugated polyene content is 4.0% by mass or more.

[0024] <Ethylene-α-olefin-nonconjugated polyene copolymer (A)> The ethylene-α-olefin-nonconjugated polyene copolymer (A) used in the present invention (hereinafter also simply referred to as "polymer (A)") is an ethylene-α-olefin-nonconjugated polyene copolymer comprising structural units derived from ethylene, structural units derived from at least one α-olefin having 3 or more carbon atoms (preferably 20 or less), and structural units derived from at least one nonconjugated polyene.

[0025] 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 individually or in combination of two or more. Among these, α-olefins with 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.

[0026] Examples of non-conjugated polyenes include linear 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, and 5-isopropylidene-2-norbornene. Examples include cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 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, and 4-ethylidene-8-methyl-1,7-nonadien. These non-conjugated polyenes may be used individually or in combination of two or more. Among these, cyclic non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, and mixtures of 5-vinyl-2-norbornene are preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being more preferred.

[0027] Copolymer (A) includes ethylene-propylene-1,4-hexadiene copolymer, ethylene-1-pentene-1,4-hexadiene copolymer, ethylene-1-hexene-1,4-hexadiene copolymer, ethylene-1-heptene-1,4-hexadiene copolymer, ethylene-1-octene-1,4-hexadiene copolymer, ethylene-1-nonene-1,4-hexadiene copolymer, ethylene-1-decene-1,4-hexadiene copolymer, and ethylene-propylene-1-octene-1,4-hexadiene copolymer. Diene copolymer, 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 copolymer, ethylene-propylene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-pentene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-hexene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, ethylene-1-heptene-5-ethylidene-2-norbornene Examples include 5-vinyl-2-norbornene copolymer, 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, and ethylene·propylene·1-octene·5-ethylidene-2-norbornene·5-vinyl-2-norbornene copolymer.

[0028] Copolymer (A) may be used alone or in combination of two or more types. Copolymer (A) satisfies the following requirements (a1) to (a4).

[0029] (a1) The weight-average molecular weight is 350,000 or more. (a2) The intrinsic viscosity [η] is 4.0 dL / g or greater. (a3) The ethylene content is 57.0% by mass or more. (a4) The non-conjugated polyene content is 4.0% by mass or more.

[0030] The lower limit of the weight-average molecular weight (Mw) of 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, preferably 600,000 or less. These upper and lower limits can be combined arbitrarily. Copolymers (A) with an Mw of less than 350,000 tend not to achieve the desired heat aging resistance.

[0031] The lower limit of the intrinsic viscosity [η] of copolymer (A), as measured in decalin at 135°C, is 4.0 dL / g or higher, preferably 4.1 dL / g or higher, and more preferably 4.2 dL / g or higher. The upper limit of the intrinsic viscosity [η] is not particularly limited, but is preferably 10.0 dL / g or lower, and more preferably 8.0 dL / g or lower. These upper and lower limits can be combined arbitrarily. If the intrinsic viscosity is less than 4.0 dL / g, the desired heat aging resistance tends not to be obtained.

[0032] The ethylene content of 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.

[0033] The lower limit of the unconjugated polyene content of 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 unconjugated polyene content of copolymer (A) can be 5.0% by mass or less. These upper and lower limits can be combined in any way.

[0034] The ethylene content and non-conjugated polyene content of copolymer (A) will be described later. 13 It is determined by 13C-NMR spectroscopy. If the ethylene content of copolymer (A) is less than 57.0% by mass, or the non-conjugated polyene content is less than 4.0% by mass, the desired heat aging resistance tends not to be obtained.

[0035] The copolymer (A) may consist solely of monomers derived from fossil fuels, solely of monomers derived from biomass, or in combination of monomers derived from fossil fuels and monomers derived from biomass. Fossil fuels are petroleum, coal, natural gas, shale gas, or combinations thereof. Biomass refers to all renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, of plant or animal origin.

[0036] (Method of manufacturing copolymer (A)) Copolymer (A) can be produced, for example, by the method described in

[0028] -

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

[0037] <Crystalline polyolefin (B)> The crystalline polyolefin (B) is not particularly limited as long as it is a crystalline polymer obtained from an olefin, but it is preferably a polymer consisting of 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. Crystalline polyolefin (B) may consist solely of monomers derived from fossil fuels, solely of monomers derived from biomass, or in combination of monomers derived from fossil fuels and monomers derived from biomass.

[0038] Crystalline polyolefin (B) may be obtained by conventionally known methods, or a commercially available product may be used. Crystalline polyolefin (B) may be used alone or in combination of two or more types.

[0039] Examples of olefins used as raw materials for crystalline polyolefins (B) include α-olefins with 2 to 20 carbon atoms (excluding propylene), 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. These may be used individually or in combination of two or more.

[0040] Among crystalline polyolefins (B), propylene-based (co)polymers, which are propylene homopolymers or propylene copolymers obtained from olefins mainly composed of propylene, are preferred in terms of heat resistance and oil resistance, and propylene homopolymers are more preferred in terms of tensile breaking strength. 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 olefins that become structural units derived from monomers other than propylene are preferably α-olefins having 2 to 20 carbon atoms (excluding propylene), more preferably ethylene and butene.

[0041] The polymerization method can be random or block-based. The melt flow rate (MFR) (ASTM D1238-65T, 230°C, 2.16 kg load) of crystalline polyolefin (B) is typically 8.0 g / 10 min or less, preferably 0.05 to 5.0 g / 10 min, and more preferably 0.1 to 4.0 g / 10 min from the viewpoint of elastic modulus. When the MFR exceeds 8.0 g / 10 min, the moldability (extrusion processability) tends to be poor.

[0042] The melting point (Tm) of crystalline polyolefin (B), obtained by differential scanning calorimetry (DSC), is typically 100°C or higher, preferably 105°C or higher, and more preferably 150-170°C. A melting point within this range allows for the development of physical properties (hardness, mechanical properties, and moldability) suitable for the purposes of the present invention. This melting point value is obtained under the following conditions.

[0043] <Measurement conditions> Approximately 5 mg of the sample is placed in a dedicated aluminum pan, and a differential scanning calorimeter (e.g., DSCPyris1 or DSC7 from PerkinElmer Corporation) is used to heat the sample from 30°C to 200°C at a rate of 320°C / min, hold it at 200°C for 5 minutes, then cool it from 200°C to 30°C at a rate of 10°C / min, hold it at 30°C for another 5 minutes, and then heat it again at a rate of 10°C / min. The melting point is determined from the endothermic curve obtained during this process. If multiple peaks are detected during DSC measurement, the peak temperature detected at the highest temperature is defined as the melting point (Tm).

[0044] Crystalline polyolefin (B) plays a role in improving the fluidity and heat resistance of the thermoplastic elastomer composition. Crystalline polyolefin (B) is typically used in a ratio of 360 to 460 parts by mass, preferably 370 to 460 parts by mass, and more preferably 370 to 420 parts by mass, per 100 parts by mass of copolymer (A). On the other hand, if the amount of crystalline polyolefin (B) is less than the above range, the hardness of the thermoplastic elastomer composition or its molded article will be low, and if it is more than the above range, the moldability (extrusion processability) of the thermoplastic elastomer composition will be poor.

[0045] <Softener (C)> As the softening agent (C), a softening agent commonly used for rubber can be used. The softening agent (C) may be a non-bio oil, which is an oil obtained from fossil raw materials, or a bio oil, which is an oil obtained from animal or plant raw materials. Examples of softeners (C) include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, 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; fatty acids or fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and zinc laurate; naphthenic acid; pine oil, rosin, or derivatives thereof; synthetic polymers such as terpene resins, petroleum resins, atactic polypropylene, and coumarone indene resin; ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, and hydrocarbon-based synthetic lubricants. Among these, process oils and paraffin oils with a solubility parameter in the range of 6.1 to 7.1 are preferred.

[0046] Among these, petroleum-based softeners are preferred, and paraffin oil is particularly preferred. The softener (C) contained in the thermoplastic elastomer composition (I) (hereinafter referred to as softener (C1)) is usually used in a proportion of 80 parts by mass or more, preferably 90 parts by mass or more, usually 140 parts by mass or less, preferably 120 parts by mass or less, and more preferably 110 parts by mass or less, per 100 parts by mass of copolymer (A). The upper and lower limits can be arbitrarily combined. Using the softening agent (C1) in this amount results in excellent fluidity during composition preparation and molding, is less likely to degrade the mechanical properties of the resulting molded article, and the resulting molded article exhibits excellent heat resistance and heat aging resistance.

[0047] <Fatty acid-based lubricant (D)> As the fatty acid-based lubricant (D), known fatty acid-based lubricants commonly found in plastics can be used. For example, those described on pages 1037-1038 of the Chemical Handbook, Applied Edition, Revised 2nd Edition (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd. in 1973) can be used. A specific example is fatty acid amide.

[0048] Specific examples of the aforementioned fatty acid amides include: Monoamides of higher fatty acids such as stearamide, oxystearoamide, oleylamide, erucicamide (also known as erucic acid amide), laurylamide, palmitylamide, and behenamide; Amides of higher fatty acids such as methylolamide, methylenebisstearoamide, ethylenebisstearoamide, ethylenebisoleylamide, and ethylenebislaurylamide; Complex amides such as stearyloleylamide, N-stearylerucamide, and N-oleylpalmitamide; and Examples include special fatty acid amides marketed under the trade names Plastrozin and Plastrozin S (Fujisawa Pharmaceutical Co., Ltd.). These may be used individually or in combination of two or more types.

[0049] Among these, monoamides of higher fatty acids are preferred, and erucic acid amides are more preferred. The fatty acid-based lubricant (D) is typically used in a ratio of 2 to 6 parts by mass, preferably 3 to 5 parts by mass, per 100 parts by mass of copolymer (A). Using the fatty acid-based lubricant (D) in this amount results in good mechanical properties and moldability of the thermoplastic elastomer composition of the present invention.

[0050] <Phenolic resin-based crosslinking agent (E)> The phenolic resin crosslinking agent (E) (also referred to as "crosslinking agent (E)" in the present invention) is a resol resin and is preferably produced by condensation of alkyl-substituted phenol or unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde, or by condensation of difunctional phenol dialcohols. For alkyl-substituted phenols, alkyl-substituted compounds with 1 to 10 carbon atoms are preferred. Furthermore, dimethylolphenols or phenolic resins substituted with alkyl groups having 1 to 10 carbon atoms at the para position are preferred. The phenolic resin curing resin is typically a thermocrosslinkable resin and is also called a phenolic resin crosslinking agent or phenolic resin. The crosslinking agent (E) usually functions to crosslink copolymer (A).

[0051] Examples of phenolic resin-based curing resins (phenolic resin-based crosslinking agents) include those represented by the following general formula [E1].

[0052] [ka] (In the formula, Q is a divalent group selected from the group consisting of -CH2- and -CH2-O-CH2-, m is 0 or a positive integer from 1 to 20, and R' is an organic group.) 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.

[0053] Specifically, examples include alkylphenol formaldehyde resins, methylolated alkylphenol resins, halogenated alkylphenol resins, and the like, with halogenated alkylphenol resins being preferred, and more preferably those in which the terminal hydroxyl groups are brominated. An example of a phenol resin-based curing resin in which the terminals are brominated is represented by the following general formula [E2].

[0054] [ka] (In the formula, n is an integer between 0 and 10, and R is a saturated hydrocarbon group with 1 to 15 carbon atoms.)

[0055] Examples of the aforementioned phenolic resin-based curing resins include Tackiroll® 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Tackiroll® 250-I (brominated alkylphenol formaldehyde resin with a bromination rate of 4%, manufactured by Taoka Chemical Industry Co., Ltd.), Tackiroll® 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (manufactured by Gun-ei Chemical Industry Co., Ltd.), Vulkaresat 510E (manufactured by Hoechst), Vulkaresat 532E (manufactured by Hoechst), and Vulkaresen E (manufactured by Hoechst), Vulkaresen 105E (manufactured by Hoechst), Vulkaresen 130E (manufactured by Hoechst), Vulkaresol 315E (manufactured by Hoechst), Amberol ST 137X (manufactured by Rohm & Haas), Sumilight Resin (registered trademark) PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphorm-C-100 (manufactured by Anchor Chem.), Symphorm-C-1001 (manufactured by Anchor Chem.), Tamanol (registered trademark) 531 (manufactured by Arakawa Chemical Co., Ltd.), Schenectady SP1059 (manufactured by Schenectady Chem.), Schenectady SP1045 (manufactured by Schenectady Chem.), CRR-0803 (manufactured by UCC), Schenectady Examples include SP1055F (manufactured by Schenectady Chem., a brominated alkylphenol formaldehyde resin), Schenectady SP1056 (manufactured by Schenectady Chem.), CRM-0803 (manufactured by Showa Union Synthetic Co., Ltd.), and Vulkadur A (manufactured by Bayer). Among these, halogenated phenol resin crosslinking agents are preferred, and brominated alkylphenol formaldehyde resins such as Tackirol® 250-I, Tackirol® 250-III, and Schenectady SP1055F can be used more preferably.

[0056] Furthermore, specific examples of crosslinking thermoplastic vulcanized rubber with phenolic resin are described in U.S. Patent No. 4,311,628, U.S. Patent No. 2,972,600, and U.S. Patent No. 3,287,440, and these technologies can also be used in the present invention.

[0057] U.S. Patent No. 4,311,628 discloses a phenolic curative system comprising a phenolic curing resin and a cure activator. The basic components of this system are formed by the condensation of a substituted phenol (e.g., halogen-substituted phenol, C1-C2 alkyl-substituted phenol) or an unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium, or by the condensation of a bifunctional phenol dialcohol (preferably with a C5-C2 atom at the para position). 10This is a phenolic resin crosslinking agent produced by the condensation of alkyl-substituted dimethylolphenols. Halogenated alkyl-substituted phenolic resin crosslinking agents produced by halogenation of alkyl-substituted phenolic resin crosslinking agents are particularly suitable. Phenolic resin crosslinking agents comprising a methylolphenol curable resin, a halogen donor, and a metal compound are particularly recommended, and their details are described in U.S. Patents No. 3,287,440 and No. 3,709,840. Non-halogenated phenolic resin crosslinking agents are used simultaneously with a halogen donor, preferably with a hydrogen halide scavenger. Normally, halogenated phenolic resin crosslinking agents, preferably brominated phenolic resin crosslinking agents containing 2 to 10% by mass of bromine, do not require a halogen donor, but are used simultaneously 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 typically used in amounts of 1 to 20 parts by mass per 100 parts by mass of the phenolic resin crosslinking agent. The presence of such scavengers promotes the crosslinking action of the phenolic resin crosslinking agent, but if the copolymer (A) is not easily crosslinked by the phenolic resin crosslinking agent (E), it is desirable to use both a halogen donor and zinc oxide. Methods for producing halogenated phenolic curable resins and their use in vulcanizing agent systems using zinc oxide are described in U.S. Patents No. 2,972,600 and No. 3,093,613, respectively, and their disclosures, along with those of U.S. Patents No. 3,287,440 and No. 3,709,840, are incorporated herein by reference. Examples of suitable halogen donors include, for example, stannous chloride, ferric chloride, or halogen-donating polymers such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and polychlorobutadiene (neoprene rubber).Suitable phenolic resin crosslinking agents and brominated phenolic resin crosslinking agents are commercially available. For example, such crosslinking agents can be purchased from Schenectady Chemicals, Inc. under trade names "SP-1045," "CRJ-352," "SP-1055F," and "SP-1056." Similar functionally equivalent phenolic resin crosslinking agents can also be obtained from other suppliers.

[0058] Phenolic resin-based crosslinking agent (E) is a suitable crosslinking agent from the viewpoint of preventing fogging because it generates few decomposition products. In the present invention, when heat treatment is performed in the presence of a crosslinking agent (E), auxiliary agents such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N,4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylenedimaleimide, polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be added.

[0059] Furthermore, a dispersion accelerator may be used to promote the decomposition of the crosslinking agent (E). Examples of decomposition accelerators include tertiary amines such as triethylamine, tributylamine, and 2,4,6-tri(dimethylamino)phenol; naphthenates of naphthenic acid with various metals (e.g., Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, rare earth elements), such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, and mercury.

[0060] The crosslinking agent (E) is typically used in a ratio of 2 to 9 parts by mass, preferably 2.5 to 8.5 parts by mass, per 100 parts by mass of copolymer (A). Using the crosslinking agent (E) in this amount results in good mechanical properties and moldability of the thermoplastic elastomer composition of the present invention. Furthermore, there are no particular limitations on the degree of crosslinking of copolymer (A) in the present invention, but it can be adjusted by changing the amount of crosslinking agent (E) within the range of the present invention.

[0061] <Optional additives> In addition to the components described above, the composition of the present invention may also contain additives to the extent that they do not impair the effects of the present invention. Examples of the aforementioned additives include colorants, antioxidants, inorganic fillers, reinforcing agents, anti-aging agents (stabilizers), processing aids, activators, hygroscopic agents, foaming agents, foaming aids, the aforementioned crosslinking aids, and the aforementioned decomposition accelerators. These additives may be used individually or in combination of two or more.

[0062] When any additives are added, the amount of stabilizers (antioxidants, anti-aging agents), processing aids, etc., is, for example, 0.01 to 0.80 parts by mass, preferably 0.10 to 0.50 parts by mass, per 100 parts by mass of copolymer (A). There are no particular restrictions on the amount of colorants, inorganic fillers, reinforcing agents, activators, hygroscopic agents, foaming agents, foaming aids, the crosslinking aids mentioned above, the decomposition accelerators mentioned above, etc., 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, per 100 parts by mass of copolymer (A).

[0063] [Thermoplastic elastomer composition (I) and method for producing the same] The thermoplastic elastomer composition (I) according to the present invention is It contains the copolymer (A) crosslinked with a phenolic resin-based crosslinking agent (E), and The crystalline polyolefin (B) is added in an amount of 360 to 460 parts by mass. The softening agent (C1) is 80 parts by mass or more, and The product contains 2 to 6 parts by mass of the fatty acid-based lubricant (D) (provided that the amount of copolymer (A) is 100 parts by mass).

[0064] The thermoplastic elastomer composition (I) according to the present invention has a half-crystallization time of 200 seconds or less at 120°C, preferably 190 seconds or less, more preferably 180 seconds or less, and the lower limit may be, for example, 60 seconds. In compositions where the half-crystallization time at 120°C exceeds 200 seconds, crystallization of crystalline polyolefin (B) in a molded article containing the composition is difficult, and the penetration pathway of the softener in the molded article becomes larger. As a result, the retention of the softener decreases, and the heat aging resistance is poor. The 1 / 2 crystallization time is the time it takes to reach 50% of the total heat energy, where the area between the DSC calorimetry curve and the baseline during the isothermal crystallization process represents the total heat energy. [See New Polymer Experiment Course 8: Properties of Polymers (Kyoritsu Shuppan Co., Ltd.)] The 1 / 2 crystallization time is measured using a differential scanning calorimetry (DSC) method, as described later.

[0065] The half-crystallization time of composition (I) at 120°C can be adjusted by the components contained in the composition, such as the type and amount of crosslinking agent, whether the ethylene-α-olefin-non-conjugated polyene copolymer used as a raw material for composition (I) is an oil-extractable product, and if it is an oil-extractable product, the amount of oil it is extruded. Since composition (I) has good heat aging resistance and extrudeability, the ethylene-α-olefin-non-conjugated polyene copolymer (A) is preferably an oil-extractable product, and its oil extruded amount is preferably 80 phr or more, and more preferably 100 phr or more.

[0066] The maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) according to 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, for example, 2 μm or more or 3 μm or more. In compositions in which the maximum spherulite size of the polyolefin component exceeds 8 μm, the molded article containing the composition becomes rough, and the penetration pathways for the softener in the molded article become larger. As a result, the retention of the softener decreases, and the heat aging resistance may be poor. In addition, the enlargement of the spherulites of the polyolefin component causes irregularities on the surface of the molded article, resulting in poor moldability, specifically extrusion processability. Furthermore, the minimum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) according to the present invention is preferably in the range of 1 to 4 μm, and more preferably in the range of 2 to 3 μm. The maximum and minimum spherulite sizes of the polyolefin components in composition (I) can be adjusted by the type and amount of components contained in the composition, such as the ethylene-α-olefin-non-conjugated polyene copolymer, the amount of oil applied if it is an oil-applied product, the type and amount of crystalline polyolefin, the type and amount of crosslinking agent, the type and amount of softener, and the injection method. More specifically, it can be controlled by the injection method of the softener, by dispersing the softener in the ethylene-α-olefin-non-conjugated polyene copolymer and suppressing the softener content in the crystalline polyolefin, thereby suppressing inhibition of crystallization of the crystalline polyolefin and controlling the spherulite size. The maximum and minimum spherulite size values ​​mentioned above were obtained by measuring using the method employed in the examples described later.

[0067] The thermoplastic elastomer composition (I) according to the present invention can be obtained by a method comprising the following steps (β). Step (β): A mixture (α) containing 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 optionally the softener (C1) per 100 parts by mass of the copolymer (A). However, the total amount of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in step (β) is 80 parts by mass or more. The mass fraction of the softener (C1) contained in the mixture (α) and the total amount of the softener (C1) optionally mixed in step (β) is usually 60 to 100% by mass, preferably 95 to 100% by mass. When this mass fraction is within this range, the half crystallization time at 120°C and the maximum spherulite size of the olefin component of the thermoplastic elastomer composition (I) can be kept within the desired range, thereby achieving both heat aging resistance and extrudeability. The mixture (α) may be the commercially available copolymer (A) that has been oil-distributed with the softener (C1). Furthermore, the above process (β) Prior to this, a step (α) may be performed in which the copolymer (A) and the softening agent (C1) are kneaded together to prepare the mixture (α).

[0068] In a method for producing a thermoplastic elastomer composition (I) according to the present invention, a preferred embodiment is that step (β) includes a step of dynamically heat-treating the copolymer (A), the crystalline polyolefin (B), the softener (C1), and the fatty acid-based lubricant (D) in the presence of the phenol resin-based crosslinking agent (E).

[0069] Dynamic heat treatment is preferably carried out in a closed-type apparatus and preferably in an inert gas atmosphere such as nitrogen or carbon dioxide. The heat treatment temperature is usually in the range of 300°C from the melting point of copolymer (A), preferably 150 to 280°C, and more preferably 170 to 270°C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes.

[0070] The dynamic heat treatment of the mixture can be carried out using conventionally known kneading equipment. Examples of such kneading equipment include mixing rolls, intensive mixers (e.g., Banbury mixers, pressure kneaders), and single-screw or twin-screw extruders, with closed-type kneading equipment being preferred and twin-screw extruders being particularly preferred.

[0071] Since the thermoplastic elastomer composition (I) according to the present invention uses the copolymer (A) and the crosslinking agent (E) as raw materials, in the heat-treated product obtained by dynamically heat-treating these raw materials, the copolymer (A) is usually crosslinked.

[0072] When producing the thermoplastic elastomer composition (I) according to the present invention, the copolymer (A), the crosslinking agent (E), and at least a portion of the crystalline polyolefin (B) may be dynamically heat-treated. However, the entire amount of the crystalline polyolefin (B) may be subjected to the dynamic heat treatment. The softener (C1), the fatty acid-based lubricant (D), and any additives may be dynamically heat-treated together with at least a portion of the copolymer (A), the crosslinking agent (E), and the crystalline polyolefin (B), respectively, or they may be mixed with the heat-treated product, or both (i.e., a portion is dynamically heat-treated and the remainder is mixed with the heat-treated product). The thermoplastic elastomer composition (I) according to the present invention is preferably a composition containing paraffin oil as the softening agent (C1).

[0073] [Molded products and their uses] The molded article according to the present invention is characterized by containing the thermoplastic elastomer composition (I) according to the present invention. The molded article according to the present invention can be formed from the thermoplastic elastomer composition (I) according to the present invention. Conventional known molding methods can be applied as the molding method. The molded article according to the present invention has excellent sliding performance and processability. The laminate of the present invention can be preferably applied not only to glass run channels but also to articles such as window frame seals and building material gaskets.

[0074] [Laminates and their applications] The laminate according to the present invention is characterized by comprising a layer containing the thermoplastic elastomer composition (I) according to the present invention (i.e., a layer that is a molded article according to the present invention) and a layer containing a soft material, which are laminated together.

[0075] Examples of the soft material include a soft material having a Type A hardness of 50 to 95, preferably 50 to 85. The Type A hardness of the soft material is measured by a method compliant with ISO 7619, which will be described later. The aforementioned soft material is not particularly limited as long as it is a material with a Type A hardness of 50 to 95, but examples 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 according to the present invention.

[0076] The thermoplastic elastomer composition (II) preferably includes the thermoplastic elastomer composition (I) according to the present invention, the thermoplastic elastomer composition (I) according to the present invention in which the phenolic resin-based crosslinking agent (E) is replaced with another crosslinking agent, and the thermoplastic elastomer compositions in which the blending ratio of the raw materials is changed. The thermoplastic elastomer composition (II) is more preferably one in which the crosslinking agent is a phenolic resin-based crosslinking agent (E).

[0077] As the thermoplastic elastomer composition (II), more preferably, 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, and propylene·ethylene copolymer to this) (Y), and 5 to 50 parts by mass of an oil-based softening agent (Z) [(the total of (X), (Y), and (Z) is 100 parts by mass)] are dynamically heat-treated in the presence of a crosslinking agent. Here, the components (X), (Y), and (Z) respectively mean the same components as the components (B), (A), and (C) used in the thermoplastic elastomer composition (I) of the present invention.

[0078] The mass fraction (W c ) of the softening agent in the thermoplastic elastomer composition used in the present invention is defined as follows. That is, in the thermoplastic elastomer composition used in the present invention, the mass ratio of the softening agent (C) to the total mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A), crystalline polyolefin (B), softening agent (C), and crosslinking agent (E') (the crosslinking agent (E') is a concept that also includes the phenolic resin-based crosslinking agent (E)) represented as a percentage is W c . Furthermore, W c in the thermoplastic elastomer composition (I) is represented as W 1c , and W c in the thermoplastic elastomer composition (II) is represented as W 2c .

[0079] The thermoplastic elastomer composition (II) contains a softening agent (C2) having a solubility parameter of 6.6 to 7.1. The mass fraction (W 2c ) of the softening agent (C2) in the thermoplastic elastomer composition (II) is preferably 30 to 60% by mass, more preferably 33 to 55% by mass. In this laminate, the mass fraction (W 1cThe mass fraction (W) of the softener (C2) relative to the total of the thermoplastic elastomer composition (II) 2c ) ratio (W 1c / W 2c The ratio (W) is preferably 0.50 or less, more preferably 0.40 or less. 1c / W 2c When ) is within the above range, the migration of the softening agent (oil) from the layer containing the thermoplastic elastomer composition (I) to the layer containing the soft material (thermoplastic elastomer composition (II)) is reduced, and the sliding performance of the layer containing the thermoplastic elastomer composition (I) is not impaired. 1c / W 2c There is no particular limit to the lower limit, but it is preferably 0.30, and more preferably 0.40.

[0080] The laminate of the present invention may further have layers other than the two layers described above. Depending on the application of the laminate, the thickness of the layer containing thermoplastic elastomer composition (I) is, for example, 30 μm to 1000 μm, and the thickness of the layer containing the soft material (thermoplastic elastomer composition (II)) is, for example, 0.1 mm to 3.0 mm.

[0081] The thermoplastic elastomer composition (I) and its molded article according to the present invention have excellent heat aging resistance, moderate hardness, and excellent mechanical strength. Therefore, the laminate according to the present invention using these is particularly useful for automotive sealing members (glass run channels), and it is also considered possible to reduce low-frequency noises (queues, squeaks, rattles (creaking noise, rattling noise)) that occur when the glass run channel comes into strong contact with glass at its bottom surface. The laminate of the present invention can be preferably applied not only to glass run channels but also to articles such as window frame seals and building material gaskets. [Examples]

[0082] The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. [Measurement or evaluation method] <Raw materials> The physical properties of the raw materials were measured using the following method. (Percentage of each constituent unit in ethylene-α-olefin-nonconjugated polyene copolymer) The proportion of structural units derived from ethylene, the proportion of structural units derived from α-olefin, and the proportion of structural units derived from non-conjugated polyene in ethylene-α-olefin-non-conjugated polyene copolymer are: 13 It was measured by 13C-NMR. 13 The measurement conditions for 1C-NMR are as follows: Measurements were taken using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL) at a measurement temperature of 120°C, with a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and 8000 cumulative measurements. 13 The spectrum was obtained by measuring the 1C-NMR spectrum.

[0083] (Number-average molecular weight and weight-average molecular weight) The number-average molecular weight and weight-average molecular weight of ethylene-α-olefin-unconjugated polyene copolymers were measured by gel permeation chromatography. The conditions were as follows: Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (All are 7.5mm I.D. x 30cm, manufactured by Tosoh Corporation) Column temperature: 140℃ Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer Flow rate: 1.0mL / min Sample concentration: 0.1% (w / v) Injection volume: 0.4mL Sampling time interval: 0.5 seconds Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation); #3 std set Molecular weight conversion: PS conversion / standard conversion method

[0084] (Intrinsic viscosity [η]) The intrinsic viscosity [η] of the ethylene-α-olefin-non-conjugated polyene copolymer was measured using a fully automatic intrinsic viscometer manufactured by Rigosha Co., Ltd., at a temperature of 135°C and using decalin as the measurement solvent.

[0085] (Solubility parameter) The solubility parameters for the softening agent were calculated using Fedors' parameters obtained from the Synthia module in Materials Studio.

[0086] <Thermoplastic elastomer composition> Thermoplastic elastomer compositions were measured or evaluated using the following methods. (MFR) Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the melt flow rate (MFR) of thermoplastic elastomer composition pellets was measured at 230°C and under a 10 kg load, in accordance with JIS K7112.

[0087] (Type A hardness) Using a 100t electric automatic press (manufactured by Shoji Co., Ltd.), a soft material was press-molded at 230°C for 6 minutes, and then cooled and pressed at room temperature for 5 minutes to produce a 2mm thick press sheet. Using this sheet, a Type A measuring instrument was used in accordance with ISO 7619, and the scale was read immediately after contact with the indenter. When the measured Type A hardness was between 50 and 95, the soft material was considered to be the soft material according to the present invention.

[0088] (Type D hardness) A 20cm x 20cm x 2mm sheet sample, prepared from a pellet of thermoplastic elastomer composition using a 50t press, was used as the test sample. The hardness was measured using a durometer type D hardness tester in accordance with JIS K 6252-3.

[0089] (Tensile properties) A 20cm x 20cm x 2mm sheet sample, prepared from a pellet of thermoplastic elastomer composition using a 50t press, was used as the test sample. Tensile tests were performed in accordance with JIS 6251 at a temperature of 25°C and a tensile speed of 500mm / min, and M100 (stress at 100% elongation), TB (tensile breaking strength), and EB (tensile elongation at breaking point) were measured.

[0090] (1 / 2 crystallization time) The half-crystallization time was measured when a pellet of thermoplastic elastomer composition was heated to 230°C at a heating rate of 500°C / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC), held for 10 minutes, and then cooled to 120°C at a cooling rate of 500°C / min.

[0091] (Maximum spherulite size and minimum spherulite size) The polyolefin component in the laminates prepared in the examples was stained with RuO4, and thin sections cut in the TD direction were carbon-deposited. Five randomly selected locations within the laminate were observed using a transmission microscope (TEM) at 10,000x magnification. The diameters of the largest and smallest polyolefin spherulites within the observation range were measured, and their average values ​​were defined as the maximum and minimum spherulite sizes. A single spherulite was defined as the area enclosed by the boundary of the white area (crystalline resin component) that was not stained by the dye. If the spherulite was not circular (i.e., elliptical or polygonal), the maximum and minimum values ​​measured horizontally or vertically on the cut surface (i.e., Figures 1 and 2) were defined as the maximum and minimum spherulite sizes.

[0092] (Heat aging resistance) The laminates produced in the examples were left in air at 85°C for 168 hours. The surface condition of the sliding layer (thermoplastic elastomer composition (I)) of the laminate was then visually inspected and tactilely examined and compared with the surface condition before the inspection. The meanings of the symbols in Tables 2 and 3 are as follows. ○: No change in surface condition △: The surface became glossy, but not sticky. ×: The surface became glossy and sticky.

[0093] (Extrusion processability) The extrusion processability of the thermoplastic elastomer composition was visually evaluated based on its appearance when laminated and extruded together with the aforementioned soft material. Those without problems were evaluated as good, while those exhibiting abnormalities such as surface roughness were evaluated as poor.

[0094] [Raw materials] As the ethylene-α-olefin-nonconjugated polyene copolymer, the ethylene-propylene-diene copolymer (hereinafter referred to as "EPDM") shown below was used. EPDM-1 Product name: Mitsui EPT (trademark) X-3042E (manufactured by Mitsui Chemicals, Inc.) EPDM-2 (trademark) KEP902NP (manufactured by KUMHO POLYCHME) EPDM-3 Product Name: Mitsui EPT (trademark) 3072EPM (manufactured by Mitsui Chemicals, Inc.) EPDM-4 Product Name: Mitsui EPT (trademark) 4100E (manufactured by Mitsui Chemicals, Inc.) Table 1 shows the physical properties of the EPDM included in EPDM-1 to EPDM-4 above. EPDM-1 to EPDM-4 are so-called oil-spreading products, which are EPDM blended with a softening agent. In Table 1, the amount of softening agent per 100 parts by mass of EPDM is listed as "oil spread amount".

[0095] [Table 1]

[0096] As crystalline polyolefin (B), the following propylene homopolymers, PP-1 to PP-3, manufactured by known techniques, were used. PP-1: MFR (230℃, 2.16kg load) = 0.5g / 10min, propylene homopolymer with a melting point of 160℃. PP-2: MFR (230℃, 2.16kg load) = 2.0g / 10min, propylene homopolymer with a melting point of 160℃. PP-3: MFR (230℃, 2.16kg load) = 9.0g / 10min, propylene homopolymer with a melting point of 160℃. Furthermore, the following ingredients were used. • Softener: PW90 (product name, manufactured by Idemitsu Kosan Co., Ltd.) (paraffin oil) • Lubricant: Erucic acid amide • Crosslinking agent: Brominated alkylphenol formaldehyde resin (product name, SP-1055F, manufactured by Schenectady) • Coloring agent: Carbon black masterbatch (manufactured by DIC Corporation, F23287MM) • Antioxidants: A mixture of phenolic antioxidant (Irganox 1010 (manufactured by BASF Japan Ltd.)), benzotriazole UV absorber (Tinuvin 326 (manufactured by BASF Japan Ltd.)), and hindered amine (HALS) weather stabilizer (Tinuvin 770 (manufactured by BASF Japan Ltd.)).

[0097] [Example 1] (Preparation of Thermoplastic Elastomer Composition-1) EPDM-1, PP-1, a softener, a lubricant, a crosslinking agent, a colorant, and an antioxidant were introduced into a twin-screw extruder (manufactured by Kobe Steel, Ltd., HYPER KTX 46) in the proportions listed in Table 2. These were melt-kneaded under the following conditions: cylinder temperature: 50-250°C (i.e., the dynamic heat treatment temperature described in the section "Thermoplastic Elastomer Composition (I) and Method for Producing the Same" above is 250°C), die temperature: 200°C, screw rotation speed: 550 pm, and extrusion rate: 40 kg / hour to obtain pellets of the thermoplastic elastomer composition (hereinafter also referred to as "Thermoplastic Elastomer Composition-1"). The evaluation results are shown in Table 2.

[0098] (Manufacturing of laminates) As the material for the layer containing the soft material (thermoplastic elastomer composition (II)), the mass fraction (W) of the softener (C2) 2c Thermoplastic elastomer compositions were prepared in the form of 42% by mass (TPV-1, type A hardness 70) or 50% by mass (TPV-2, type A hardness 70).

[0099] Specifically, a thermoplastic elastomer composition (hereinafter referred to as "TPV-1") was produced by dynamically heat-treating 24 parts by mass of polyolefin resin (PP-1), 37 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (EPDM-1), and 33 parts by mass of a softening agent (C2) (solubility parameter = 7.1) in the presence of 6 parts by mass of a crosslinking agent (brominated alkylphenol formaldehyde resin) under the same conditions as when producing the thermoplastic elastomer composition-1 described above. Furthermore, a thermoplastic elastomer composition (hereinafter referred to as "TPV-2") was produced by dynamically heat-treating 19 parts by mass of polyolefin resin (PP1), 33 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (EPDM-1), and 42 parts by mass of a softening agent (C2) (solubility parameter = 7.1) in the presence of 6 parts by mass of a crosslinking agent (brominated alkylphenol formaldehyde resin) under the same conditions as when producing thermoplastic elastomer composition-1 described above.

[0100] Using a co-extrusion apparatus, a laminate (sliding layer thickness 200-250 μm, total laminate thickness 2 mm) was fabricated by laminating a layer containing a soft material (TPV-1 or TPV-2) and a sliding layer containing thermoplastic elastomer composition-1. Table 2 shows the results of the heat aging resistance evaluation using this laminate as the test sample.

[0101] [Examples 2-8, Comparative Examples 1-6] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1, except that the type or amount of raw materials was changed as shown in Table 1, and then a laminate was prepared. The evaluation results are shown in Tables 2 and 3.

[0102] [Table 2]

[0103] [Table 3]

Claims

1. The product includes a crosslinked product of an ethylene-α-olefin-non-conjugated polyene copolymer (A) (where the α-olefin has 3 or more carbon atoms) that satisfies the following requirements (a1) to (a4) and a phenol resin-based crosslinking agent (E), and Amount to 100 parts by mass of the copolymer (A): 360 to 460 parts by mass of crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 min or less as measured under conditions of 230°C and a 2.16 kg load, Fatty acid-based lubricant (D) in 2 to 6 parts by mass, and A thermoplastic elastomer composition (I) containing 80 parts by mass or more of a softening agent (C1), The half-crystallization time of the thermoplastic elastomer composition (I) at 120°C is 200 seconds or less. A thermoplastic elastomer composition (I) wherein the maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) is in the range of 8 μm or less. (a1) The weight-average molecular weight is 350,000 or more. (a2) The intrinsic viscosity [η] is 4.0 dL / g or greater. (a3) The ethylene content is 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), as measured by differential calorimetry, is 150 to 170°C.

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

4. A layer comprising the thermoplastic elastomer composition (I) according to claim 1 or 2, A laminate comprising layers containing a soft material having a Type A hardness of 50 to 95 as measured in accordance with ISO 7619.

5. The laminate according to claim 4, wherein the hardness of type A of the soft material is 50 to 85.

6. The soft material includes 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 mass fraction (W) of the softener (C2) relative to the total of the thermoplastic elastomer composition (II) ２Ｃ The laminate according to claim 4, wherein ) is 30 to 60% by mass.

7. The mass fraction (W) of the softener (C1) relative to the total amount of the thermoplastic elastomer composition (I) １Ｃ ) of the aforementioned W ２Ｃ Ratio to (W １Ｃ / W ２Ｃ The laminate according to claim 6, wherein ) is 0.5 or less.

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), The thermoplastic elastomer composition (I) satisfies the following requirements (X) and (Y), A step (α) to prepare a mixture (α) by kneading an ethylene-α-olefin-non-conjugated polyene copolymer (A) (where the number of carbon atoms in the α-olefin is 3 or more) that satisfies the following requirements (a1) to (a4) with a softening agent (C1), and The mixture (α) and Amount to 100 parts by mass of the copolymer (A): 360 to 460 parts by mass of crystalline polyolefin (B) having a melt flow rate of 8.0 g / 10 min or less as measured under conditions of 230°C and a 2.16 kg load, A phenolic resin-based crosslinking agent (E) is provided in 2 to 9 parts by mass, Fatty acid-based lubricant (D) is 2 to 6 parts by mass, The process includes a step (β) of optionally mixing with a softening agent (C1), The total amount of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in step (β) is 80 parts by mass or more. A method for producing a thermoplastic elastomer composition (I), wherein the mass fraction of the softener (C1) contained in the mixture (α) and the softener (C1) optionally mixed in step (β) is 60 to 100% by mass. (X) The half-crystallization time of thermoplastic elastomer composition (I) at 120°C is 200 seconds or less. (Y) The maximum spherulite size of the polyolefin component contained in the thermoplastic elastomer composition (I) is in the range of 8 μm or less. (a1) The weight-average molecular weight is 350,000 or more. (a2) The intrinsic viscosity [η] is 4.0 dL / g or greater. (a3) The ethylene content is 57.0% by mass or more. (a4) The non-conjugated polyene content is 4.0% by mass or more.

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

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

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