Sliding composition and use thereof, and method for producing sliding composition

Abstract

One embodiment of the present invention relates to a sliding composition film or a method for producing a sliding composition; the sliding composition contains an ethylene / α-olefin / non-conjugated polyene copolymer (A), a propylene random copolymer (B1) and a propylene homopolymer (B2) that each have a melt flow rate (MFR) of 0.1 to 4.0 g / 10 min, a high density polyethylene (C1) that has a density of 940 to 970 kg / m3 and an MFR of 0.1 g / 10 min or less, an ultra high molecular weight polyethylene (C2) that has a limiting viscosity (η) of 10 to 40 dl / g (at 135°C in decalin), an average particle diameter D50 of 22 to 50 µm and a density of less than 940 kg / m3, and a silicone compound (D) that has a kinematic viscosity of 3,000 to 1,000,000 cSt (at 25°C), respectively in specific amounts; and at least some of the copolymer (A) is crosslinked by a phenolic resin-based crosslinking agent.

Description

Sliding composition, its use, and method for producing the sliding composition

[0001] One aspect of the present invention relates to a sliding composition, uses of the sliding composition, or a method for producing the sliding composition.

[0002] Olefin-based thermoplastic elastomers are lightweight, easily recyclable, and do not emit toxic gases when incinerated, and therefore, from the viewpoints of energy conservation, resource conservation, and more recently, global environmental protection, they are widely used in automobile parts, industrial machinery parts, electric and electronic parts, building materials, etc. Glass run channels are an example of such automobile parts.

[0003] A glass run channel is a sealing material (guiding member) placed between the window glass and the window frame, and is required to slide smoothly against the glass. Conventional products for this purpose include thermoplastic elastomer compositions containing a silicone-based additive or fine particles made of polyethylene or the like in a thermoplastic elastomer (compositions with sliding properties are sometimes referred to as "sliding compositions" in particular).

[0004] Patent Document 1 describes a configuration (Example 8) in which the glass sliding layer bonded to the glass run channel body contains high-density polyethylene, a non-polar elastomer, and a lubricant (silicone masterbatch).

[0005] Patent Document 2 describes that a glass run channel made of a composition in which a silylated polyolefin is blended with a thermoplastic elastomer has excellent adhesion and abrasion resistance between the substrate layer and the surface layer.

[0006] Patent Document 3 describes that a glass run channel made of a composition in which fine particles made of high-density polyethylene and a silicone masterbatch are blended with a thermoplastic elastomer has excellent appearance, coefficient of friction, and sliding properties.

[0007] Japanese Patent Application Laid-Open No. 10-193985 Japanese Patent Application Laid-Open No. 2015-189088 Japanese Patent No. 6976862

[0008] However, when the inventors investigated the extrusion moldability of olefin-based thermoplastic elastomer compositions (sliding compositions) containing silicone-based additives and polyethylene microparticles, they found that formulations containing silicone-based additives can cause problems with corner adhesion and that foreign matter called "eye gunk" adheres to the die of the molding machine, impairing processability. They also found that significant surface irregularities occur on the molded product, impairing its appearance. Furthermore, they found that there is room for improvement in heat aging resistance and sliding properties.

[0009] One aspect of the present invention provides a sliding composition that can be used to produce molded articles such as glass run channels that have both sliding properties and corner adhesion and are excellent in balance between extrusion moldability, appearance, and heat aging resistance, and a method for producing the sliding composition.

[0010]

[0023] The following are examples of the composition of the present invention: [1] 7.0% by mass or more of an ethylene-α-olefin-non-conjugated polyene copolymer (A), 6.0% by mass or more of a propylene random copolymer (B1) having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, 10.0% by mass or more of a propylene homopolymer (B2) having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, and a density of 940 to 970 kg / m 3 and 15.0 mass % or more of a high-density polyethylene (C1) having a melt flow rate of 0.1 g / 10 min or less measured at 190°C under a load of 2.16 kgf, and an intrinsic viscosity [η] measured in a decalin solvent at 135°C of 10 to 40 dl / g and an average particle diameter D 50 is 22 to 50 μm, and the density is 940 kg / m 3and 5.0 to 8.0 mass % of a silicone compound (D) having a kinematic viscosity at 25°C of 3,000 to 1,000,000 cSt (provided that the total content of the components (A), (B1), (B2), (C1), (C2) and (D) is 100.0 mass % or less), wherein at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked with a phenolic resin-based crosslinking agent.

[0011] [2] The sliding composition according to [1], further comprising 0.1 to 10.0 mass % of a softener (E) (provided that the total content of the components (A), (B1), (B2), (C1), (C2), (D), and (E) is 100.0 mass % or less), wherein the ethylene-α-olefin-non-conjugated polyene copolymer (A) has a weight average molecular weight of 280,000 or more, an intrinsic viscosity [η] measured in decalin at 135°C of 3.4 dl / g or more, a content of ethylene-derived structural units of 70 mass % or less (provided that the total content of the ethylene-derived structural units and the α-olefin-derived structural units is 100 mass %), and a content of non-conjugated polyene-derived structural units of 6.0 mass % or less of all structural units of the copolymer (A).

[0012] [3] The sliding composition according to [1] or [2], which has a Shore D hardness (after 5 seconds) measured in accordance with ISO 7619 of 30 to 60.

[0013] [4] The sliding composition according to any one of [1] to [3], wherein the content of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is 7.0 to 10.0 mass %.

[0014] [5] The sliding composition according to any one of [1] to [4], wherein the total content of the propylene random copolymer (B1) and the propylene homopolymer (B2) is 20.0 mass % or more.

[0015] [6] The content of the propylene-based random copolymer (B1) is 9.0 to 15.0 mass%, and the density of the propylene-based random copolymer (B1) is 900 to 920 kg / m 3The sliding composition according to any one of [1] to [5],

[0016] [7] The content of the propylene homopolymer (B2) is 10.0 to 18.0 mass%, and the density of the propylene homopolymer (B2) is 900 to 920 kg / m 3 The sliding composition according to any one of [1] to [6], wherein

[0017] [8] The sliding composition according to any one of [1] to [7], wherein the mass ratio of the propylene homopolymer (B2) to the propylene random copolymer (B1), [(B2) / (B1)], is 1.0 to 3.0.

[0018] [9] The content of the ultra-high molecular weight polyethylene (C2) is 10.0 to 30.0 mass%, and the average particle diameter D 50 [9] The sliding composition according to any one of [1] to [8], wherein the particle size is 22 to 30 μm.

[0019]

[10] A molded article obtained by molding the sliding composition according to any one of [1] to [9].

[0020]

[11] A glass run channel comprising the molded article according to

[10] .

[0021]

[12] An ethylene / α-olefin / non-conjugated polyene copolymer (A) of 7.0% by mass or more, a propylene random copolymer (B1) of 6.0% by mass or more having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, a propylene homopolymer (B2) of 10.0% by mass or more having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, and a density of 940 to 970 kg / m 3 and 15.0 mass % or more of a high-density polyethylene (C1) having a melt flow rate of 0.1 g / 10 min or less measured at 190°C under a load of 2.16 kgf, and an intrinsic viscosity [η] measured in a decalin solvent at 135°C of 10 to 40 dl / g and an average particle diameter D 50 is 22 to 50 μm, and the density is 940 kg / m 3and 5.0 to 8.0 mass % of a silicone compound (D) having a kinematic viscosity of 3,000 to 1,000,000 cSt at 25°C (provided that the total content of the components (A), (B1), (B2), (C1), (C2) and (D) is 100.0 mass % or less), and at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked, the method for producing the sliding composition comprising the step of crosslinking at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) with a phenolic resin-based crosslinking agent.

[0022] The sliding composition according to one embodiment of the present invention can provide both sliding properties and corner adhesion, and can produce molded articles such as glass run channels that are excellent in balance between extrusion moldability, appearance, and heat aging resistance.

[0023] One embodiment of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0024] <<Sliding Composition>> The sliding composition according to one embodiment of the present invention (hereinafter also simply referred to as "the composition") comprises: an ethylene-α-olefin-non-conjugated polyene copolymer (A); a propylene-based random copolymer (B1) having a melt flow rate (MFR) of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf; a propylene homopolymer (B2) having a MFR of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf; and a propylene homopolymer (B3) having a density of 940 to 970 kg / m. 3 and a high-density polyethylene (C1) having an MFR of 0.1 g / 10 min or less as measured at 190°C under a load of 2.16 kgf; a high-density polyethylene (C2) having an intrinsic viscosity [η] of 10 to 40 dl / g as measured in decalin solvent at 135°C and an average particle diameter D 50 is 22 to 50 μm, and the density is 940 kg / m 3and a silicone compound (D) having a kinematic viscosity at 25° C. of 3,000 to 1,000,000 cSt. The composition is characterized in that at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked with a phenolic resin-based crosslinking agent.

[0025] The content of component (A) in the present composition is 7.0% by mass or more, preferably 7.0 to 10.0% by mass, more preferably 7.0 to 9.0% by mass, and even more preferably 7.0 to 8.0% by mass, based on 100.0% by mass of the present composition.

[0026] The content of component (B1) in the composition is 6.0% by mass or more, preferably 6.0 to 15.0% by mass, more preferably 6.0 to 13.0% by mass, and even more preferably 6.0 to 11.0% by mass, based on 100.0% by mass of the composition. The content of component (B2) in the composition is 10.0% by mass or more, preferably 10.0 to 18.0% by mass, more preferably 12.0 to 17.5% by mass, and even more preferably 13.0 to 17.0% by mass, based on 100.0% by mass of the composition. The total content of components (B1) and (B2) is preferably 20.0% by mass or more, more preferably 20.0 to 25.0% by mass, based on 100.0% by mass of the composition. The mass ratio of component (B1) to component (B2) [(B2) / (B1)] is preferably 1.0 to 3.0, and more preferably 1.2 to 2.8.

[0027] The content of component (C1) in the composition is 15.0% by mass or more, preferably 15.0 to 40.0% by mass, more preferably 20.0 to 40.0% by mass, and even more preferably 25.0 to 35.0% by mass, based on 100.0% by mass of the composition. The content of component (C2) in the composition is 10.0% by mass or more, preferably 10.0 to 30.0% by mass, more preferably 10.0 to 25.0% by mass, and even more preferably 10.0 to 20.0% by mass, based on 100.0% by mass of the composition. The total content of components (C1) and (C2) is preferably 30.0% by mass or more, more preferably 30.0 to 50.0% by mass, based on 100.0% by mass of the composition. The mass ratio of component (C1) to component (C2) [(C2) / (C1)] is preferably 0.1 to 1.0, and more preferably 0.2 to 0.7.

[0028] The content of component (D) in the present composition is 5.0 to 8.0 mass%, preferably 5.5 to 8.0 mass%, more preferably 6.0 to 8.0 mass%, and even more preferably 6.0 to 7.5 mass%, based on 100.0 mass% of the present composition. The total content of components (A), (B1), (B2), (C1), (C2), and (D) is 100.0 mass% or less.

[0029] By blending (containing) the components (A), (B1), (B2), (C1), (C2), and (D) in the above-mentioned proportions, the present composition can produce a molded article that achieves both good sliding properties and good adhesion at corners, and that also has an excellent balance of extrusion moldability, appearance, heat aging resistance, and the like.

[0030] If the amount of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is less than the lower limit, the resin loses flexibility and wrinkles easily; if the amount exceeds the upper limit, the sliding properties tend to deteriorate. If the amount of each propylene-based resin (B) is less than the lower limit, moldability deteriorates; if the amount exceeds the upper limit, the resin loses flexibility and wrinkles easily. If the amount of the high-density polyethylene (C1) is less than the lower limit, the sliding properties deteriorate; if the amount exceeds the upper limit, the resin becomes hard and wrinkles easily. If the amount of the ultra-high molecular weight polyethylene (C2) is less than the lower limit, the elongation decreases and the low-temperature properties deteriorate; if the amount exceeds the upper limit, the resin softens and the sliding properties deteriorate. If the amount of the silicone compound (D) is less than the lower limit, the sliding properties deteriorate; if the amount exceeds the upper limit, the adhesiveness of the corners of the resulting molded article decreases and the low-temperature impact strength also tends to deteriorate. Each component will be described in detail below.

[0031] [Ethylene-α-olefin-non-conjugated polyene copolymer (A)] The ethylene-α-olefin-non-conjugated polyene copolymer (A) is a copolymer containing structural units derived from ethylene, an α-olefin other than ethylene, and a non-conjugated polyene. The composition may contain only one type of copolymer (A), or may contain two or more types.

[0032] The α-olefin is typically an α-olefin having 3 to 20 carbon atoms, and specific examples include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1, and 12-ethyltetradecene-1. Among these, propylene, 1-butene, 4-methylpentene-1, 1-hexene, and 1-octene are preferred, with propylene being particularly preferred. These α-olefins may be used alone or in combination of two or more.

[0033] Specific examples of the non-conjugated polyenes include linear non-conjugated dienes such as 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene; Examples of suitable non-conjugated dienes include cyclic non-conjugated dienes such as bornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, and norbornadiene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nonadiene. Among these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nonadiene are preferred.

[0034] The monomers constituting the copolymer (A) (for example, ethylene, an α-olefin other than ethylene, and a non-conjugated polyene) may be only monomers obtained from a biomass-derived raw material, may be only monomers obtained from a fossil fuel-derived raw material, or may be a mixture of monomers obtained from a biomass-derived raw material and monomers obtained from a fossil fuel-derived raw material.

[0035] The content of ethylene-derived structural units in copolymer (A) is preferably 70% by mass or less, more preferably 55 to 70% by mass, and even more preferably 60 to 69% by mass, when the total of the content of ethylene-derived structural units and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100% by mass. Furthermore, when the total of the content of ethylene-derived structural units and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%, the content of ethylene-derived structural units is preferably 60 to 80 mol%, and more preferably 70 to 80 mol%.

[0036] The content of structural units derived from an α-olefin having 3 to 20 carbon atoms in copolymer (A) is preferably 30% by mass or more, more preferably 30 to 45% by mass, and even more preferably 31 to 40% by mass, when the total of the content of structural units derived from ethylene and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100% by mass. Furthermore, when the total of the content of structural units derived from ethylene and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%, the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is preferably 20 to 40 mol%, and more preferably 20 to 30 mol%.

[0037] When the content of the ethylene-derived structural units and the content of the structural units derived from an α-olefin having 3 to 20 carbon atoms are within the above ranges, the resulting sliding composition tends to have excellent mechanical properties, rubber elasticity, cold resistance, and processability. When the content of the ethylene-derived structural units is 70% by mass or less and the content of the structural units derived from an α-olefin having 3 to 20 carbon atoms is 30% by mass or more, the resulting sliding composition tends to have excellent flexibility, rubber elasticity at low temperatures, and processability. When the content of the ethylene-derived structural units is 55% by mass or more and the content of the structural units derived from an α-olefin having 3 to 20 carbon atoms is 45% by mass or less, the resulting sliding composition tends to have excellent mechanical properties and rubber elasticity at high temperatures.

[0038] Furthermore, the content of non-conjugated polyene-derived structural units in the total structural units of copolymer (A) is preferably 6.0 mass% or less, more preferably 2.0 to 6.0 mass%, and even more preferably 3.0 to 6.0 mass%. When the content of non-conjugated polyene-derived structural units is within the above range, the extrusion appearance and heat aging resistance tend to be excellent. The content of each structural unit in copolymer (A) is as follows: 13 The measurement can be performed by a C-NMR method, and peak identification and quantification can be performed according to, for example, the method described below and the method described in "Polymer Analysis Handbook" (Asakura Publishing, 2008, First Edition, pp. 184-211).

[0039] The copolymer (A) preferably has an intrinsic viscosity [η] measured in decalin at 135°C of 3.4 dl / g or more, more preferably 3.4 to 6.0 dl / g, and even more preferably 3.4 to 5.5 dl / g. When the intrinsic viscosity [η] measured in decalin at 135°C is within this range, a sliding composition having an excellent balance of mechanical properties, rubber elasticity, and processability tends to be obtained. The intrinsic viscosity [η] is measured by the method described in the Examples below.

[0040] The iodine value of the copolymer (A), measured in accordance with JIS K 0070:1992, is preferably 2 to 50 g / 100 g, more preferably 5 to 40 g / 100 g, and even more preferably 7 to 30 g / 100 g. If the iodine value is below the lower limit, the crosslinking efficiency in the thermoplastic elastomer described below may decrease, resulting in a decrease in rubber elasticity. If the iodine value is above the upper limit, the crosslinking density may become too high, resulting in a decrease in elongation and a deterioration in the balance of physical properties.

[0041] The weight-average molecular weight (Mw) of the copolymer (A) measured by GPC is preferably 280,000 or more, more preferably 280,000 to 500,000. The molecular weight distribution (Mw / Mn) is usually 1.5 to 50, preferably 1.8 to 30, more preferably 2.0 to 6. If the molecular weight distribution is below the above range, the content of low-molecular-weight components will be low, and processability may be reduced. If the molecular weight distribution is above the above range, the content of low-molecular-weight components will be high, and fogging resistance may be impaired.

[0042] The Mooney viscosity (ML) of the copolymer (A) at 100°C measured in accordance with JIS K 6395:2010 1+4 ) is preferably 15 to 400, more preferably 30 to 250. When the Mooney viscosity is within the above range, the balance between mechanical properties and processability tends to be excellent.

[0043] The copolymer (A) may be a commercially available product or may be produced by a conventionally known method, such as those described in "Polymer Production Process (Kogyo Chosakai, Inc., pp. 309-330)" or in JP-A Nos. 9-71617, 9-71618, 9-208615, 10-67823, 10-67824, 10-110054, WO 2009 / 081792, and WO 2009 / 081794, among others, all of which are filed by the applicant of the present application.

[0044] Examples of olefin polymerization catalysts preferably used in producing the copolymer (A) include: known Ziegler catalysts comprising a transition metal compound such as vanadium (V), zirconium (Zr), or titanium (Ti) and an organoaluminum compound (organoaluminum oxy compound); known metallocene catalysts comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table of the elements and an organoaluminum oxy compound or an ionizing ionic compound (e.g., the metallocene catalyst described in JP-A-9-40586); known metallocene catalysts comprising a specific transition metal compound and a co-catalyst such as a boron compound (e.g., the metallocene catalyst described in WO 2009 / 072553); and transition metal compound catalysts comprising a specific transition metal compound and an organometallic compound, an organoaluminum oxy compound, or a compound that reacts with the transition metal compound to form an ion pair (e.g., the transition metal compound catalyst described in JP-A-2011-52231). In particular, the use of a metallocene catalyst is particularly preferred because the distribution of the non-conjugated polyene becomes uniform, making it possible to obtain high crosslinking efficiency even with a small amount of non-conjugated polyene introduced, and because the catalyst activity is high and the chlorine content derived from the catalyst can be reduced.

[0045] Before being mixed with components other than the copolymer (A) described below, the copolymer (A) may be used as a component (α) containing the copolymer (A), such as a copolymer obtained by pre-mixing a petroleum-based plasticizer (softener) with the copolymer (A) to obtain an oil-extended copolymer (hereinafter also referred to as "oil-extended rubber"). Examples of the petroleum-based plasticizer include the same plasticizers as those exemplified as "petroleum-based plasticizers" in the softener (E) described below in [Other Components].

[0046] The method for producing the oil-extended rubber (oil-extending method) can be any conventionally known method, including a method of mechanically kneading the copolymer (A) and a petroleum-based plasticizer using a mixing roll or a Banbury mixer to perform oil extension, a method of adding a predetermined amount of petroleum-based plasticizer to the copolymer (A) and then removing the solvent by a method such as steam stripping, and a method of stirring a mixture of crumb-like copolymer (A) and a petroleum-based plasticizer using a Henschel mixer or the like to impregnate the copolymer.

[0047] The oil-extended rubber may be a commercially available product, and examples thereof include Mitsui EPT manufactured by Mitsui Chemicals, Inc., JSR EPR manufactured by JSR Corporation, Esprene (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., Keltan (registered trademark) manufactured by LANXESS Corporation, KEP (registered trademark) manufactured by Kumho Polychem Co., Ltd., and NODEL (registered trademark) manufactured by Dow Chemical.

[0048] [Propylene-Based Resin (B)] The present composition contains a propylene-based random copolymer (B1) and a propylene homopolymer (B2) as the propylene-based resin (B). The propylene-based random copolymer (B1) is a copolymer of propylene and an α-olefin (propylene-α-olefin copolymer), and is a random copolymer. The present composition may contain only one type of copolymer (B1) and one type of polymer (B2), or two or more types of copolymer (B1) and one type of polymer (B2).

[0049] <Propylene-Based Random Copolymer (B1)> Examples of the α-olefin in the propylene-α-olefin copolymer (B1) include ethylene and α-olefins having 4 to 12 carbon atoms. Examples of the α-olefins having 4 to 12 carbon atoms include linear or branched α-olefins such as 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene-1-decene, and 1-dodecene. One or more of the α-olefins may be used.

[0050] The content of propylene-derived structural units in copolymer (B1) is preferably 60 to 99.5 mol%, more preferably 80 to 99 mol%, even more preferably 90 to 98.5 mol%, and particularly preferably 95 to 98 mol%. Furthermore, the content of α-olefin-derived structural units in the propylene-α-olefin copolymer is preferably 0.5 to 40 mol%, more preferably 1 to 20 mol%, even more preferably 1.5 to 10 mol%, and particularly preferably 2 to 5 mol%. The sum of the content of propylene-derived structural units and the content of α-olefin-derived structural units is 100 mol%.

[0051] The propylene-α-olefin copolymer may also contain a small amount (e.g., 10 mol % or less based on the total structural units of the propylene copolymer (A)) of structural units derived from other olefins other than ethylene and those having a carbon number of 3 to 12. One type of such other olefin may be used, or two or more types may be used.

[0052] The melt flow rate (MFR) of copolymer (B1) is 0.1 to 4.0 g / 10 min, preferably 0.3 to 2.5 g / 10 min, and more preferably 0.5 to 2.0 g / 10 min, as measured at 190°C under a load of 2.16 kgf in accordance with JIS K 7210. When copolymer (B1) has an MFR within the above range, the composition can be easily injection-molded, and a molded article having excellent dimensional stability and impact strength in a well-balanced manner can be easily obtained.

[0053] The density of the copolymer (B1) according to JIS K 7112 B method (pycnometer method) is preferably 900 to 920 kg / cm 3 , more preferably 910 to 920 kg / cm 3 When the density of the copolymer (B1) is within the above range, the composition can be easily injection molded, and a molded article having a good balance between dimensional stability and impact strength can be easily obtained.

[0054] <Propylene Homopolymer (B2)> The melt flow rate (MFR) of the polymer (B2), measured in accordance with JIS K 7210 at 190°C under a load of 2.16 kgf, is 0.1 to 4.0 g / 10 min, preferably 0.3 to 2.5 g / 10 min, and more preferably 0.5 to 2.0 g / 10 min. When the MFR of the polymer (B2) is within the above range, the composition can be easily injection-molded, and a molded article having excellent dimensional stability and impact strength in a well-balanced manner can be easily obtained.

[0055] The density of the polymer (B2) measured in accordance with JIS K7112 B method (pycnometer method) is preferably 900 to 920 kg / cm 3 , more preferably 910 to 920 kg / cm 3When the density of the polymer (B2) is within the above range, the composition can be easily injection molded, and a molded article having a good balance between dimensional stability and impact strength can be easily obtained.

[0056] The copolymer (B1) and the polymer (B2) may be commercially available products or may be appropriately produced by known methods. The monomers constituting the copolymer (B1) and / or the polymer (B2) (e.g., propylene, an α-olefin other than propylene) may consist solely of monomers obtained from a biomass-derived raw material, may consist solely of monomers obtained from a fossil fuel-derived raw material, or may be a mixture of monomers obtained from a biomass-derived raw material and monomers obtained from a fossil fuel-derived raw material.

[0057] The composition may contain a propylene-based polymer (B3) other than the copolymer (B1) and the polymer (B2) within the range that does not impair the effects of the present invention. For example, a propylene-based block copolymer (e.g., a block copolymer of propylene and 30 mol % or less of another α-olefin) can be mentioned.

[0058] Commercially available propylene-based resins (B) include, for example, Prime Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd., Novatec (registered trademark) manufactured by Japan Polypropylene Corporation, and Sumitomo (registered trademark) Noblen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0059] [Ethylene-Based Resin (C)] The present composition contains, as the ethylene-based resin (C), a high-density polyethylene (C1) and an ultra-high molecular weight polyethylene (C2). The high-density polyethylene (C1) is a component for achieving both adhesiveness and sliding properties, and the ultra-high molecular weight polyethylene (C2) is a component for achieving both extrusion moldability and sliding properties. The present composition may contain only one type of high-density polyethylene (C1) and one type of ultra-high molecular weight polyethylene (C2), or may contain two or more types of high-density polyethylene (C1) and one type of ultra-high molecular weight polyethylene (C2).

[0060] <High-density polyethylene (C1)> Examples of high-density polyethylene (C1) include ethylene homopolymers and ethylene-α-olefin copolymers. Specific examples of the α-olefin in the ethylene-α-olefin copolymer include α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. One or more of the α-olefins may be used.

[0061] When the high-density polyethylene (C1) is an ethylene-α-olefin copolymer, the content of ethylene-derived structural units is preferably 50 to 99 mol%, more preferably 55 to 99 mol%, and even more preferably 55 to 98 mol%, and the content of α-olefin-derived structural units is preferably 1 to 50 mol%, more preferably 1 to 45 mol%, and even more preferably 2 to 45 mol%, where the sum of the content of ethylene-derived structural units and the content of α-olefin-derived structural units is 100 mol%.

[0062] The density of high-density polyethylene (C1) measured in accordance with JIS K7112 B method (pycnometer method) is 940 to 970 kg / cm 3 , preferably 945 to 965 kg / cm 3 When the density of the high-density polyethylene (C1) is within the above range, a molded article having excellent adhesiveness can be easily obtained.

[0063] The melting point of the high-density polyethylene (C1) measured by differential scanning calorimetry (DSC) is preferably 110 to 150°C, more preferably 115 to 150°C, and even more preferably 120 to 140°C, from the viewpoint of adhesiveness. Here, the melting point is the crystalline melting peak temperature (Tm) determined from a thermogram measured using a differential scanning calorimeter, in which about 10 mg of a sample is heated from -40°C to 200°C at a heating rate of 10°C / min, held at 200°C for 1 minute, cooled to -40°C at a cooling rate of 10°C / min, and then heated again to 200°C at a heating rate of 10°C / min.

[0064] The MFR of the high-density polyethylene (C1), measured in accordance with JIS K 7210 at 190°C under a load of 2.16 kgf, is 0.1 g / 10 min or less, preferably 0.01 to 0.1 g / 10 min, and more preferably 0.01 to 0.50 g / 10 min, from the viewpoint of improving sliding properties, etc.

[0065] Examples of polymerization catalysts used in the production of the high-density polyethylene (C1) include known multi-site catalysts such as Ziegler and Phillips catalysts, Kaminsky catalysts such as zirconocene, titanocene, and hafnocene (collectively referred to as metallocene), and highly active single-site catalysts such as post-metallocene catalysts. The high-density polyethylene (C1) can be produced by a known polymerization method using such a polymerization catalyst.

[0066] <Ultra-high molecular weight polyethylene (C2)> Examples of the ultra-high molecular weight polyethylene (C2) include ethylene homopolymers and ethylene-α-olefin copolymers. Specific examples of the α-olefin in the ethylene-α-olefin copolymer include α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. One or more of the α-olefins may be used.

[0067] When the ultra-high molecular weight polyethylene (C2) is an ethylene-α-olefin copolymer, the content of ethylene-derived structural units is preferably 50 to 99 mol%, more preferably 55 to 99 mol%, and even more preferably 55 to 98 mol%, and the content of α-olefin-derived structural units is preferably 1 to 50 mol%, more preferably 1 to 45 mol%, and even more preferably 2 to 45 mol%. Here, the sum of the content of ethylene-derived structural units and the content of α-olefin-derived structural units is 100 mol%.

[0068] The intrinsic viscosity [η] of the ultra-high molecular weight polyethylene (C2) measured in decalin at 135°C is 10 to 40 dl / g, preferably 15 to 35 dl / g, and more preferably 20 to 35 dl / g, from the viewpoint of improving sliding properties, etc. The intrinsic viscosity [η] is measured by the method described in the examples below.

[0069] Average particle diameter D of ultra-high molecular weight polyethylene (C2) 50 is 22 to 50 μm, more preferably 22 to 40 μm, and even more preferably 22 to 30 μm. The average particle size is measured by the method described in the Examples below. When the average particle size of the ultra-high molecular weight polyethylene (C2) is within the above range, a molded product with excellent extrusion moldability can be easily obtained. The average particle size [η] is measured by the method described in the Examples below.

[0070] The density of the ultra-high molecular weight polyethylene (C2) measured in accordance with JIS K7112 B method (pycnometer method) is 940 kg / cm 3 less than 850 to 930 kg / cm 3 , more preferably 850 to 920 kg / cm 3 When the density of the ultra-high molecular weight polyethylene (C2) is within the above range, a molded article having excellent extrusion moldability can be easily obtained.

[0071] The ultra-high molecular weight polyethylene (C2) can be produced by a known polymerization method using an olefin polymerization catalyst. For example, it is preferable to produce it by solution polymerization, slurry polymerization, high-pressure ionic polymerization, or gas-phase polymerization using a Ziegler-Natta catalyst or a complex catalyst such as a metallocene complex or a non-metallocene complex, or by bulk polymerization or solution polymerization using a radical initiator. Among these, it is particularly preferable to use a method of polymerizing a monomer using a Ziegler-Natta catalyst or a complex catalyst, or a method of polymerizing a monomer in the presence of a metallocene catalyst.

[0072] The monomers (e.g., ethylene, α-olefins other than ethylene) constituting the high-density polyethylene (C1) and / or the ultra-high-molecular-weight polyethylene (C2) may consist solely of monomers obtained from biomass-derived raw materials, or may consist solely of monomers obtained from fossil fuel-derived raw materials, or may be a mixture of monomers obtained from biomass-derived raw materials and monomers obtained from fossil fuel-derived raw materials.

[0073] The composition may contain an ethylene polymer (C3) other than the high-density polyethylene (C1) and the ultra-high molecular weight polyethylene (C2) to the extent that the effects of the present invention are not impaired. Commercially available ethylene resins (C) include, for example, Hi-Zex (registered trademark) manufactured by Prime Polymer Co., Ltd., Mipelon (registered trademark) manufactured by Mitsui Chemicals, Inc., Mirason (registered trademark) manufactured by Prime Polymer Co., Ltd., Evolue (registered trademark) manufactured by Prime Polymer Co., Ltd., and Suntec (registered trademark) manufactured by Asahi Kasei Corporation.

[0074] [Silicone Compound (D)] The present composition contains a silicone compound (D). The silicone compound (D) is a component added mainly to reduce sliding resistance. The present composition may contain only one type of silicone compound (D), or may contain two or more types of silicone compound (D).

[0075] From the viewpoint of reducing sliding resistance, the kinematic viscosity of the silicone compound (D) at 25°C is 3,000 to 1,000,000 cSt, preferably 3,000 to 500,000 cSt, and more preferably 3,000 to 200,000 cSt. When multiple types of silicone compound (D) are used, it is sufficient that the kinematic viscosity at 25°C of each of them is within the above range. The kinematic viscosity is measured by the method described in the examples below.

[0076] Examples of the silicone compound (D) include silicone oil, high molecular weight silicone (silicone gum), and silicone powder. (D-1) Silicone oil, preferably having a kinematic viscosity of 5000 mm 2 It is preferable to use a silicone oil having a viscosity of less than 1 / s in combination with the silicone gum (D-2).

[0077] When the silicone oil (D-1) and the silicone gum (D-2) are used in combination, the mass blending ratio [(D-1) / (D-2)] is preferably 90 / 10 to 10 / 90, more preferably 75 / 25 to 25 / 75.

[0078] Examples of silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, alkyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, and modified silicone oil.

[0079] The silicone gum preferably has a weight-average molecular weight of 100,000 or more, more preferably 100,000 to 800,000, and even more preferably 450,000 to 650,000. Non-crosslinked silicone gums are also preferred. The weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0080] The silicone gum may be a commercially available product, or a commercially available silicone masterbatch in which the silicone gum is pre-mixed with a resin component such as polypropylene, etc. Examples of commercially available products include MB50-001 and BY27-001 manufactured by Dow Corning Toray Co., Ltd., CF-9150 manufactured by Dow Corning Toray Silicone Co., Ltd., and X-21-3043 and X-22-2101 manufactured by Shin-Etsu Chemical Co., Ltd.

[0081] The GPC measurement of the silicone gum in the masterbatch can be carried out by first subjecting the masterbatch to the treatment described below, for example, to separate it into silicone gum and polypropylene, and then measuring the resulting silicone gum.

[0082] (Separation of Silicone Gum and Polypropylene) First, 0.05 g of the sample (masterbatch) is weighed out, and 10 mL of xylene containing 0.1 g / L BHT (dibutylhydroxytoluene) is added. The mixture is then stirred at 125°C for 60 minutes to dissolve the masterbatch. After visually confirming that the masterbatch has completely dissolved, the solution is left to stand at room temperature for approximately 3 hours to precipitate crystalline polypropylene in the liquid. The solution from which the crystals have precipitated is suction filtered using a Sumitomo Electric Fluoropore FP-100 (1 μm) filter and washed with 3 mL of xylene to separate it into CXS (xylene-soluble fraction, silicone gum) and CXIS (xylene-insoluble fraction, polypropylene). The CXS is pre-dried by nitrogen blowing at room temperature and then vacuum-dried at 60°C. Vacuum drying is continued until no weight loss is observed. GPC measurement is performed using the CXS fraction after vacuum drying.

[0083] [Other Components] The present composition may contain other components in addition to the above-described (A) to (D), as necessary, to the extent that the effects of the present invention are not impaired. Examples of such other components include resins or elastomers other than the above-described (A) to (C), softeners (E), heat stabilizers, antistatic agents, weather stabilizers, antioxidants, UV absorbers, light stabilizers, fillers, flame retardants, colorants, and lubricants. These other components may each be used alone or in combination of two or more.

[0084] <Softener (E)> As the softener (E), a softener (plasticizer) typically used for rubber can be used. The softener (E) may be a softener obtained from a raw material derived from a fossil fuel, or may be a softener obtained from an animal or plant-based raw material.

[0085] Specific examples of the softener (E) include petroleum-based plasticizers such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based plasticizers such as coal tar and coal tar pitch; fatty oil-based plasticizers such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; sab (factice); waxes such as beeswax, carnauba wax, and lanolin; fatty acids and 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 polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadine, liquid thiokol, and hydrocarbon-based synthetic lubricating oils. Among these, petroleum-based plasticizers, particularly process oils, such as paraffin-based process oils and naphthene-based process oils, are preferably used.

[0086] When the softener (E) is blended into the present composition, the blending amount (content) thereof is preferably 0.1 to 10.0 mass%, more preferably 1.0 to 9.8 mass%, based on 100.0 mass% of the present composition, from the viewpoints of bleeding suppression and coating adhesion. However, the total content of the components (A), (B1), (B2), (C1), (C2), (D), and (E) is 100.0 mass% or less. When the oil-extended rubber is used as a raw material for the present composition, the petroleum-based plasticizer used for oil extension is included in the softener (E).

[0087] <<Method for Producing the Composition>> The composition can be produced by melt-kneading the ethylene-α-olefin-non-conjugated polyene copolymer (A), the propylene-based random copolymer (B1), the propylene homopolymer (B2), the high-density polyethylene (C1), the ultra-high-molecular-weight polyethylene (C2), the silicone compound (D), and, as necessary, other components, followed by granulation or pulverization.

[0088] The present composition is characterized in that at least a portion of the copolymer (A) is crosslinked with a phenolic resin-based crosslinking agent. That is, the method for producing the composition includes a step of crosslinking at least a portion of the copolymer (A) with a phenolic resin-based crosslinking agent. The step is not particularly limited as long as it is a conventionally known crosslinking method using a phenolic resin-based crosslinking agent, but from the viewpoints of sliding properties, low-temperature properties, and flexibility, it is preferably as follows: A method in which a mixture containing the copolymer (A), the phenolic resin-based crosslinking agent, preferably a portion of the propylene-based resin (B), and optionally other components is dynamically heat-treated to produce a thermoplastic elastomer in which at least a portion of the copolymer (A) is partially or completely crosslinked with the phenolic resin-based crosslinking agent (hereinafter also simply referred to as "thermoplastic elastomer"), and then the remaining propylene-based resin (B), high-density polyethylene (C1), ultra-high molecular weight polyethylene (C2), silicone compound (D), and optionally other components are melt-kneaded and then granulated or pulverized.

[0089] The kneading can be carried out using a kneading device, and examples of the kneading device include a mixing roll, an intensive mixer (e.g., a Banbury mixer, a kneader), a single-screw or twin-screw extruder, etc., but a non-open type device is preferred. The granulation or pulverization can be carried out by a conventionally known method.

[0090] [Thermoplastic elastomer] The raw material of the present composition may be a thermoplastic elastomer prepared in advance as described above, in which at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is partially or completely crosslinked with a phenolic resin-based crosslinking agent. The thermoplastic elastomer may also contain a propylene-based resin (B).

[0091] Examples of such thermoplastic elastomers include the following (1) and (2): (1) a partially or completely crosslinked thermoplastic elastomer obtained by dynamically heat-treating a mixture containing (a) a crosslinked olefin copolymer rubber (uncrosslinked rubber) (e.g., copolymer (A)) [hereinafter also referred to as "component (a)"], (b) a crystalline polypropylene (e.g., propylene resin (B)) [hereinafter also referred to as "component (b)"], and, if necessary, (c) a petroleum-based plasticizer [hereinafter also referred to as "component (c)"] in the presence of a phenolic resin-based crosslinking agent; (2) a partially or completely crosslinked thermoplastic elastomer obtained by dynamically heat-treating a mixture containing component (a), a portion of component (b), and, if necessary, component (c) in the presence of a phenolic resin-based crosslinking agent, and then uniformly blending (d) the remaining component (b) into a crosslinked rubber composition.

[0092] The petroleum-based plasticizer (c) is a high-boiling petroleum fraction that is generally used to weaken the intermolecular forces of rubber when roll-processing the rubber, making it easier to process, and to aid in the dispersion of optional carbon black, white carbon, etc., or to reduce the hardness of the vulcanized rubber and increase its flexibility and elasticity. Examples of component (c) include plasticizers similar to the petroleum-based plasticizers listed in the "Other Components" above.

[0093] In the thermoplastic elastomer, the mass ratio of the component (b) to the component (a) [(b) / (a)] is usually 90 / 10 to 10 / 90, preferably 70 / 30 to 15 / 85.

[0094] Furthermore, as component (a), copolymer (A) may be used in combination with other uncrosslinked rubber. In this case, the other uncrosslinked rubber is used in an amount of preferably 40 parts by mass or less, more preferably 5 to 20 parts by mass, per 100 parts by mass of the total amount of component (b) and component (a). Examples of the other uncrosslinked rubber include diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), and butyl rubber (IIR), SEBS, and polyisobutylene.

[0095] The thermoplastic elastomer preferably contains a propylene-based resin (B) as the crystalline polypropylene and an ethylene-α-olefin-non-conjugated polyene copolymer (A) as the uncrosslinked rubber, in which these exist in a partially crosslinked state in the thermoplastic elastomer, and in which the mass blending ratio of the crystalline polypropylene to the uncrosslinked rubber [crystalline polypropylene / uncrosslinked rubber] is within the range of 70 / 30 to 10 / 90.

[0096] A more specific example of the thermoplastic elastomer includes a thermoplastic elastomer in which the uncrosslinked rubber (a-1) is partially crosslinked, which is obtained by dynamically heat-treating a mixture containing 30 to 90 parts by mass of at least one uncrosslinked rubber (a-1) selected from ethylene-propylene-non-conjugated polyene copolymers, 70 to 10 parts by mass of at least one crystalline polypropylene (b-1) selected from propylene-based random copolymers (B1) (where the total amount of components (a-1) and (b-1) is 100 parts by mass), and 5 to 150 parts by mass of a petroleum-based plasticizer (c) in the presence of a phenolic resin-based crosslinking agent.

[0097] The phenolic resin-based crosslinking agent is a thermally crosslinkable resin, also called a phenolic resin-based cured resin or a phenolic resin. Examples of the phenolic resin-based crosslinking agent include halogenated phenolic resin-based crosslinking agents. By using the phenolic resin-based crosslinking agent, a sliding composition having excellent heat aging resistance can be obtained.

[0098] Suitable examples of phenolic resin-based crosslinking agents include, for example, resol resins, crosslinking agents produced by condensing alkyl-substituted or unsubstituted phenols with aldehydes, preferably formaldehyde, in an alkaline medium, or crosslinking agents produced by condensing difunctional phenol dialcohols.

[0099] The alkyl-substituted phenol is preferably a substituted phenol having an alkyl group of about 1 to 10 carbon atoms, and more preferably a dimethylolphenol or phenol resin substituted at the para position with an alkyl group of about 1 to 10 carbon atoms.

[0100] Examples of phenolic resin-based crosslinking agents include compounds represented by the following formula (I) or compounds in which the terminal hydroxyl group (—CH—OH) of the compound represented by the following formula (I) has been substituted with a halogen atom.

[0101] (wherein Q is —CH— or —CH—O—CH—, m is an integer of 0 to 20, and R′ is an organic group.)

[0102] Preferably, Q is —CH—O—CH—, m is an integer from 0 to 10, and R′ is an organic group having less than 20 carbon atoms. More preferably, m is an integer from 0 to 5, and R′ is an organic group having 4 to 12 carbon atoms.

[0103] Specific examples of the compound represented by formula (I) or a compound in which the terminal hydroxyl group (-CH-OH) of the compound represented by formula (I) is substituted with a halogen atom include alkylphenol formaldehyde resins, methylolated alkylphenol resins, and halogenated alkylphenol resins, with halogenated alkylphenol resins being preferred, and bromides in which the terminal hydroxyl group (-CH-OH) of the compound represented by formula (I) is substituted with a bromine atom being more preferred. An example of such a bromide is shown in formula (II) below.

[0104] (wherein n is an integer of 0 to 10, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.)

[0105] Examples of the phenol resin-based crosslinking agent include Tackirol 201 (an alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), Tackirol 250-I (a brominated alkylphenol formaldehyde resin with a bromination rate of 4%, manufactured by Taoka Chemical Co., Ltd.), Tackirol 250-III (a brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), PR-4507 (manufactured by Gunei Chemical Industry Co., Ltd.), Vulkaresat 510E (manufactured by Hoechst), Vulkaresat 532E (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 ST 137X (manufactured by Rohm & Haas), Sumilite Resin PR-22193 (manufactured by Sumitomo Bakelite Co., Ltd.), Symphorm-C-100 (manufactured by Anchor Chem.), Symphorm-C-1001 (manufactured by Anchor Chem.), Tamanor 531 (manufactured by Arakawa Chemical Industries, Ltd.), Schenectady SP1059 (manufactured by Schenectady Chem.), Schenectady Examples of such crosslinking agents include SP1045 (manufactured by Schenectady Chem.), CRR-0803 (manufactured by U.C.C.), Schenectady SP1055 (brominated alkylphenol formaldehyde resin, manufactured by Schenectady Chem.), Schenectady SP1056 (manufactured by Schenectady Chem.), CRM-0803 (manufactured by Showa Polymer Co., Ltd.), and Vulkadur A (manufactured by Bayer). Among these, halogenated phenol resin-based crosslinking agents are preferred, and brominated alkylphenol formaldehyde resins such as Tackirol 250-I, 250-III, Schenectady SP1055, and SP1056 are more preferred.

[0106] Specific examples of crosslinking using the phenolic resin-based crosslinking agent include the techniques described in US Pat. Nos. 4,311,628, 2,972,600, and 3,287,440.

[0107] U.S. Patent No. 4,311,628 discloses a phenolic curative system consisting of a phenolic curing resin and a cure activator. The basic component of the system is a phenolic resin crosslinker produced by condensing a substituted phenol (e.g., a halogen-substituted phenol or a C1-C2 alkyl-substituted phenol) or unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium, or by condensing a difunctional phenol dialcohol (preferably a dimethylolphenol substituted with a C5-C10 alkyl group at the para position). Halogenated alkyl-substituted phenolic resin crosslinkers produced by halogenating an alkyl-substituted phenolic resin crosslinker are particularly suitable. Phenolic resin crosslinkers consisting of a methylolphenol curing resin, a halogen donor, and a metal compound are particularly recommended, and details thereof are described in U.S. Pat. Nos. 3,287,440 and 3,709,840. Non-halogenated phenolic resin crosslinkers are used simultaneously with a halogen donor, preferably together with a hydrogen halide scavenger. Halogenated phenolic resin crosslinkers, preferably brominated phenolic resin crosslinkers containing 2 to 10% by weight of bromine, typically do not require a halogen donor but are used simultaneously with a hydrogen halide scavenger such as a metal oxide selected from 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 an amount of 1 to 20 parts by weight per 100 parts by weight of the phenolic resin crosslinker. The presence of such a scavenger promotes the crosslinking action of the phenolic resin crosslinker. However, for rubbers that do not readily crosslink with phenolic resin crosslinkers, it is desirable to use both a halogen donor and zinc oxide.The preparation of halogenated phenolic curing resins and their use in crosslinker systems using zinc oxide are described in U.S. Patents 2,972,600 and 3,093,613, the disclosures of which, along with those of U.S. Patents 3,287,440 and 3,709,840, are incorporated herein by reference. Examples of suitable halogen donors include, for example, stannous chloride, ferric chloride, chlorinated paraffins, chlorinated polyethylene, chlorosulfonated polyethylene, and halogen-donating polymers such as polychlorobutadiene (neoprene rubber). For more details on phenolic vulcanizing systems, see "Vulcanization and Vulcanizing Agents" by W. Hoffman, Palmerton Publishing Company. Suitable phenolic resin-based crosslinkers are commercially available; for example, such crosslinkers can be purchased from Schenectady Chemicals, Inc. under the trade names "SP1045," "CRJ352," "SP1055," and "SP1056."

[0108] The phenolic resin-based crosslinking agent is used in an amount of preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (a). The phenolic resin-based crosslinking agent may be used in the form of a crosslinking agent masterbatch in which it is premixed with a hydrogen halide scavenger such as zinc oxide. By setting the blending amount of the phenolic resin-based crosslinking agent within the above range, a composition with excellent moldability can be easily obtained, and the resulting thermoplastic elastomer molded article has high strength, excellent oil resistance, and sufficient heat resistance and mechanical properties.

[0109] In dynamic crosslinking with the phenolic resin-based crosslinking agent, a crosslinking aid such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N,4-dinitrosoaniline, nitrosobenzene, diphenyl guanidine, or trimethylolpropane-N,N'-m-phenylenedimaleimide; a polyfunctional methacrylate monomer such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, or allyl methacrylate; or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate may be used.

[0110] By using the auxiliary, a uniform and gentle crosslinking reaction can be expected. Divinylbenzene is preferred as the auxiliary. Divinylbenzene is easy to handle, has good compatibility with the uncrosslinked rubber (a-1) and the crystalline polyolefin (b-1), and has the effect of solubilizing the phenolic resin-based crosslinking agent and acts as a dispersant for the phenolic resin-based crosslinking agent, so that the crosslinking effect by heat treatment becomes uniform, and a thermoplastic elastomer with a good balance between fluidity and physical properties can be easily obtained.

[0111] The crosslinking aid or auxiliary is used in an amount of preferably 2 parts by mass or less, more preferably 0.3 to 1 part by mass, per 100 parts by mass of the component (a).

[0112] Furthermore, in dynamic crosslinking with the phenolic resin-based crosslinking agent, a dispersion accelerator may be used to accelerate the decomposition of the phenolic resin-based crosslinking agent. Examples of the decomposition accelerator include tertiary amines such as triethylamine, tributylamine, and 2,4,6-tri(dimethylamino)phenol; naphthenates of aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury, and the like, and naphthenic acid salts of various metals (e.g., Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, and rare earth elements).

[0113] The amount of the dispersing promoter used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the total of the components (a) and (b). When the amount of the dispersing promoter used is within this range, the crosslinking reaction does not proceed too quickly, and the dispersing promoter is unlikely to remain unreacted in the resulting thermoplastic elastomer, making it possible to easily obtain a thermoplastic elastomer that has excellent flowability and is resistant to changes in physical properties due to thermal history during processing and molding.

[0114] The term "dynamic heat treatment" as used herein refers to kneading the components in a molten state. The kneading can be carried out using a kneading device, and examples of the kneading device that can be used include open-type mixing rolls and closed-type Banbury mixers, extruders, kneaders, and continuous mixers. Of these, closed-type kneading devices are preferred. The kneading is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

[0115] The kneading temperature is usually 150 to 280°C, preferably 170 to 250°C, and the kneading time is usually 0.5 to 20 minutes, preferably 1 to 10 minutes. The kneading is preferably carried out while applying a shear force, and the applied shear force is at a shear rate of 10 to 50,000 sec. -1 , preferably 100 to 20,000 seconds -1 It is desirable to set the range to

[0116] The Shore D hardness (after 5 seconds) of the thermoplastic elastomer measured in accordance with ISO 7619 is preferably 1 to 98, more preferably 1 to 60, even more preferably 10 to 50, and particularly preferably 30 to 50, in order to obtain a molded product excellent in rigidity.

[0117] The MFR of the thermoplastic elastomer measured in accordance with ASTM D1238 at 230°C under a load of 10 kgf is usually 0.1 to 100 g / 10 min, and preferably 1 to 100 g / 10 min. When the MFR is equal to or higher than the lower limit, the flowability is improved and molding in an extruder is facilitated, whereas when the MFR is equal to or lower than the upper limit, the occurrence of drawdown and the like when extruded from the nozzle of the extruder can be suppressed, resulting in good extrusion moldability.

[0118] <<Molded Article>> A molded article according to one embodiment of the present invention (hereinafter also referred to as the "present molded article") is a molded article obtained by molding the present composition. The present molded article can be produced by molding the present composition by various known molding methods, specifically, various molding methods such as extrusion molding, press molding, injection molding, calendar molding, and hollow molding. The present molded article may also be a molded article obtained by further subjecting a molded article such as a sheet obtained by the above molding method to secondary processing, such as thermoforming.

[0119] From the viewpoint of achieving excellent moldability of the present molded article, the composition preferably has an MFR of 0.1 to 100 g / 10 min, more preferably 1 to 100 g / 10 min, measured at 230°C under a load of 10 kgf in accordance with ASTM D1238. When the MFR is equal to or higher than the lower limit, the composition has good fluidity and is easily molded in an extruder, whereas when the MFR is equal to or lower than the upper limit, the occurrence of drawdown or the like when the composition is discharged from the nozzle of the extruder can be suppressed, resulting in good extrusion moldability.

[0120] The present molded article preferably has a swell value of 1.00 to 1.50, more preferably 1.03 to 1.10. When the swell value is within the above range, adhesion of resin to the die is suppressed, and processability may be improved.

[0121] In order to provide a molded article of the present invention with excellent rigidity, the Shore D hardness (after 5 seconds) of the composition of the present invention measured in accordance with ISO 7619 is preferably 30 to 60, more preferably 34 to 58, even more preferably 38 to 56, and particularly preferably 42 to 54.

[0122] The use of the molded article is not particularly limited, but suitable examples include various well-known uses such as automobile parts, civil engineering and building materials, electric and electronic parts, sanitary products, and films and sheets.

[0123] <Automobile Parts> Examples of the automobile parts include automobile interior parts and automobile exterior parts, and specific examples include weatherstrip materials, bumper moldings, side moldings, air spoilers, deflectors, mudguards, air duct hoses, wire harness grommets, rack and pinion boots, suspension cover boots, glass guides, inner belt line seals, corner moldings, glass encapsulations, hood seals, glass run channels, secondary seals, various types of packing, hoses, and airbag covers. Among these, the molded product of the present invention has an excellent balance of adhesiveness and sliding properties and also has excellent low-temperature impact strength, and is therefore particularly suitable for use in automobile parts having corners such as glass run channels.

[0124] <Civil Engineering and Building Materials> Examples of the civil engineering and building materials include ground improvement sheets, water supply boards, civil engineering materials and building materials used for noise prevention, etc., various gaskets and sheets for civil engineering and construction, water-stopping materials, joint materials, and architectural window frames.

[0125] <Electric / Electronic Parts> Examples of the electric / electronic parts include electric wire coating materials, connectors, caps, plugs, and the like.

[0126] <Hygiene Products> Examples of the hygiene products include sanitary products, disposable diapers, toothbrush grips, and the like.

[0127] <Films and Sheets> Examples of the films and sheets include infusion bags, medical containers, automobile interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort pouch containers, pipes, transparent substrates, and sealants.

[0128] The molded article can also be used for other applications besides the above-mentioned applications, such as footwear such as shoe soles and sandals, leisure goods such as swimming fins, swimming goggles, golf club grips and baseball bat grips, gaskets, waterproof fabrics, belts, garden hoses, anti-slip tape for stairs, and anti-slip tape for logistics pallets.

[0129] Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0130] <Measurement or Evaluation Method> In the following, each physical property was measured or evaluated by the following method.

[0131] [Two-Layer Sheet Molding Method] Various two-layer sheets used in the evaluation of the sliding composition were produced under the following conditions, with the type of substrate and the sheet thickness appropriately changed. For the sliding layer, pellets of the sliding composition obtained as described below were used. The substrate layer was extrusion molded using a 50 mm single-screw extruder (manufactured by The Japan Steel Works, Ltd.) under temperature conditions of [C1 / C2 / C3 / C4 / C5 = 160 / 170 / 180 / 190 / 200°C]. The sliding layer was extrusion molded using a 30 mm single-screw extruder (Plastic Engineering Research Institute, Inc.) under temperature conditions of [C1 / C2 / C3 = 200 / 210 / 230°C].

[0132] [Weight-average molecular weight] The weight-average molecular weight of the (co)polymer and silicone compound was measured by GPC under the following conditions: (Measurement conditions) Instrument: HLC-8120 manufactured by Tosoh Corporation Column: PL 10u Mixed B manufactured by Polymer Laboratories (7.5 mm ID x 30 cm x 2) Detector: Differential refractive index detector (RI / built-in) Solvent: Toluene (special grade) Temperature: 40°C Flow rate: 1.0 mL / min Injection amount: 110 μL Concentration: 0.1 mass% Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene equivalent

[0133] [Intrinsic viscosity [η] measured in decalin at 135° C.] The intrinsic viscosity [η] (dl / g) of the (co)polymer was measured in decalin at a temperature of 135° C. Specifically, about 15 mg of a sample was dissolved in 50 ml of decalin, and the specific viscosity η was measured in an oil bath at 135° C. sp After diluting this decalin solution with 5 ml of decalin, the specific viscosity η sp This dilution procedure was repeated twice, and the η when the concentration (C) was extrapolated to 0 was measured as shown in the following formula. sp The value of / C was calculated as the intrinsic viscosity [η]. [η] = lim (η sp / C) (C→0)

[0134] [Average particle diameter D 50 Average particle diameter D of ultra-high molecular weight polyethylene 50 was calculated from the weight-based particle size distribution by the Coulter counter method using a Beckman Multisizer Three.

[0135] [Melting Point (Tm)] The melting point (Tm) of the (co)polymer was measured by differential scanning calorimetry using the following method. Approximately 5 mg of a sample was placed in a dedicated aluminum pan, and using a Diamond DSC manufactured by PerkinElmer Japan Co., Ltd., the sample was heated from 30°C to 230°C at a rate of 320°C / min, held at 230°C for 10 minutes, then cooled from 230°C to 30°C at a rate of 10°C / min, held at 30°C for another 1 minute, and then heated at a rate of 10°C / min. The melting point was determined from the endothermic curve obtained during this heating. Note that when multiple peaks are detected during DSC measurement, the peak temperature detected at the highest temperature side is defined as the melting point (Tm).

[0136] [Ethylene content] The ethylene content of the copolymer is determined under the following conditions: 13C-NMR measurement was performed, and the values ​​were calculated by analyzing the obtained spectrum. Apparatus: Bruker Biospin, AVANCE III cryo-500 type nuclear magnetic resonance apparatus Measurement nucleus: C (125 MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 μ seconds) Number of points: 64 k Measurement range: 250 ppm (-55 to 195 ppm) Repetition time: 5.5 seconds Number of accumulations: 128 Measurement solvent: orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) Sample concentration: ca. 60 mg / 0.6 mL Measurement temperature: 120 ° C. Window function: exponential (BF: 1.0 Hz) Chemical shift reference: δδ signal (29.73 ppm)

[0137] [Iodine Value] The iodine value of the copolymer was measured in accordance with JIS K 0070:1992 as the iodine value (g / 100 g) of the following ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.

[0138] [Melt Flow Rate (MFR)] The MFR of each of the sliding compositions obtained below was measured at 230°C and a load of 10 kgf according to ASTM D 1238. Furthermore, the MFR of each of the raw material (co)polymers used in the following examples and comparative examples was measured at 230°C or 190°C and a load of 2.16 kgf according to JIS K 7210.

[0139] [Shore D Hardness (After 5 Seconds)] In accordance with ISO 7619, a 3 mm thick injection-molded square plate was prepared using the sliding composition obtained below. Two of the prepared 3 mm thick injection-molded square plates were stacked to form a 6 mm thick laminate sheet, and the Shore D hardness of the square plate was measured using a Shore D hardness tester. The Shore D hardness was determined 5 seconds after the measurement.

[0140] [Tensile Properties (Tensile Break Strength and Tensile Break Elongation)] A 2 mm thick pressed sheet was prepared from the sliding composition obtained below using a 50 ton press (apparatus conditions: preheating (190°C) for 8 minutes, pressing (190°C) for 6 minutes). A 2 mm thick pressed sheet was prepared. A tensile test was performed on the prepared 3 mm thick pressed sheet in accordance with JIS K 6251 using a JIS No. 3 dumbbell at a measurement temperature of 25°C and a tensile speed of 500 mm / min and 200 mm / min to measure the tensile break strength (TB) and tensile break elongation (EB).

[0141] [Sliding Properties (Dynamic Friction Coefficient and Wear Amount)] A soft thermoplastic elastomer material (C700BM manufactured by Mitsui Chemicals, Inc.) with a JIS Duro A hardness of 70° was used as a substrate. The sliding composition obtained below was laminated on the substrate to a thickness of 200 μm using an extrusion molding machine to produce a two-layer sheet. A glass piece having a thickness of 2 mm, a tip radius R of 10 mm, and a surface roughness Ra of 3.0 μm was placed on the surface of the two-layer sheet facing the sliding composition, and the sheet was slid 20,000 times under a load of 1 kg, a speed of 150 mm / sec, and a stroke of 100 mm. The dynamic friction coefficients before and after sliding were measured in accordance with ASTM D1894-63. A dynamic friction coefficient of 0.25 or less after sliding indicates excellent sliding properties. The wear amount was calculated by weighing the mass (mg) of the sliding composition before and after sliding.

[0142] [Extrusion Processability (Adhesion of Residue)] A soft thermoplastic elastomer material (C700BM manufactured by Mitsui Chemicals, Inc.) having a JIS Duro A hardness of 70° was used as a substrate, and the sliding composition obtained below was laminated on the substrate using an extrusion molding machine to a thickness of 200 to 250 μm, to produce a two-layer sheet for 30 continuous minutes. After 30 minutes of continuous molding, the extrusion processability of the sliding composition was evaluated according to the following criteria: ◯: No silicone resin was attached to the nozzle of the extrusion molding machine. ×: Silicone resin was attached to the nozzle of the extrusion molding machine.

[0143] [Extrusion Processability (Extrusion Appearance)] For the two-layer sheet produced for the evaluation of sliding properties, the surface irregularities on the side of the sliding composition before sliding were observed using a surface roughness measuring instrument (model: VR-5000, manufactured by KEYENCE), a comparative measurement module (model: VR-H3J, manufactured by KEYENCE), and a VR-5000 analysis application (manufactured by KEYENCE), and the ten-point average roughness Rz of the surface irregularities was determined. The extrusion appearance was evaluated according to the following criteria. ◯: Rz is less than 30 μm ×: Rz is 30 μm or more

[0144] [Extrusion Processability (Swell)] The pellets of the sliding composition obtained below were subjected to extrusion process using a Strograph 1D type (orifice L / D=30) manufactured by Toyo Seiki Seisakusho, Ltd., at a measurement temperature of 200° C., a preheating time of 6 minutes, and a shear rate of 122 sec. -1 The swell value was measured.

[0145] [Adhesion] A test specimen was prepared by injection molding the two-layer sheet prepared for the evaluation of sliding properties with a thermoplastic elastomer for injection bonding (Milastomer G800BS manufactured by Mitsui Chemicals, Inc.). The adhesive interface of the obtained test specimen was repeatedly bent 180°, and the number of times the test specimen was bent until a notch was formed at the end or the test specimen broke was evaluated according to the following criteria: ◯: 30 or more bends ×: Less than 30 bends

[0146] [Heat Aging Resistance] Substrate A (C700BM manufactured by Mitsui Chemicals, Inc.) having a JIS Duro A hardness of 70° and an oil-extended amount of 40 parts by mass, or substrate B (TS7000N manufactured by Mitsui Chemicals, Inc.) having a JIS Duro A hardness of 70° and an oil-extended amount of 50 parts by mass, was used as the substrate. The sliding composition obtained below was laminated on the substrate to a thickness of 200 μm using an extrusion molding machine to produce a two-layer sheet. Each of the obtained two-layer sheets was heated at 85° C. for 72 hours, and the surface of each two-layer sheet on the side of the sliding composition after heating was observed, and the changes before and after heating were evaluated according to the following criteria. ◯: No change was observed in the two-layer sheet before and after heating. ×: Changes were observed, such as bleeding, on the surface of the two-layer sheet before and after heating.

[0147] <Materials Used> As the component (α) containing the ethylene-α-olefin-non-conjugated polyene copolymer (A), the following oil-extended rubber was used. Oil-extended rubber (α-1): Mitsui EPT (registered trademark) 3072EPM (manufactured by Mitsui Chemicals, Inc.) Oil-extended rubber (α-1) is an oil-extended ethylene-propylene-5-ethylidene-2-norbornene (ENB) copolymer rubber, and is a product (oil-extended amount 40 parts by mass) obtained by oil-extending an ethylene-propylene-ENB copolymer (A-1) having an ethylene content of 64% by mass (molar equivalent value (the total of ethylene and propylene is 100 mol%); ethylene content 75.8 mol%, propylene content 24.2 mol%), an ENB content of 5.4% by mass, an iodine value of 11.5 g / 100 g, an intrinsic viscosity [η] measured in decalin at 135°C of 3.4 dl / g, and a weight-average molecular weight of 280,000. An oil-extended amount of 40 parts by mass means that 40 parts by mass of petroleum-based plasticizer (softener) is blended with 100 parts by mass of the ethylene-propylene-ENB copolymer (A-1). Oil-extended rubber (α-2): Mitsui EPT (registered trademark) 4100E (manufactured by Mitsui Chemicals, Inc.) Oil-extended rubber (α-2) is an oil-extended ethylene-propylene-ENB copolymer rubber, and is a product (oil-extended amount 50 parts by mass) obtained by oil-extending an ethylene-propylene-ENB copolymer (A-2) having an ethylene content of 57% by mass (molar equivalent value (the total of ethylene and propylene is 100 mol%); ethylene content 71 mol%, propylene content 29 mol%), an ENB content of 7.3% by mass, an iodine value of 15.4 g / 100 g, an intrinsic viscosity [η] measured in decalin at 135°C of 4.1 dl / g, and a weight-average molecular weight of 470,000. Oil-extended rubber (α-3): Mitsui EPT (registered trademark) X-3042 (manufactured by Mitsui Chemicals, Inc.) Oil-extended rubber (α-3) is an oil-extended ethylene-propylene-ENB copolymer rubber, and is a product (oil-extended amount 120 parts by mass) obtained by oil-extending an ethylene-propylene-ENB copolymer (A-3) having an ethylene content of 67% by mass (molar equivalent value (the total of ethylene and propylene is 100 mol%); ethylene content 77 mol%, propylene content 23 mol%), an ENB content of 4.3% by mass, an iodine value of 9.9 g / 100 g, an intrinsic viscosity [η] measured in decalin at 135°C of 4.3 dl / g, and a weight-average molecular weight of 350,000.

[0148] The following copolymer was used as the propylene random copolymer (B1): Copolymer (B1-1): Prime Polypro B241 (manufactured by Prime Polymer Co., Ltd.) Copolymer (B1-1) is a crystalline resin of a propylene / ethylene random copolymer, and has an MFR (according to JIS K 7210, 190°C, 2.16 kgf load) of 0.5 g / 10 min and a density of 910 kg / m 3 is.

[0149] The following polymer was used as the propylene homopolymer (B2): Homopolymer (B2-1): Prime Polypro E200GP (manufactured by Prime Polymer Co., Ltd.) The homopolymer (B2-1) had an MFR (based on JIS K 7210, 190°C, 2.16 kgf load) of 2.0 g / 10 min and a density of 900 kg / m 3 Homopolymer (B2-2): Prime Polypro E111G (manufactured by Prime Polymer Co., Ltd.) Homopolymer (B2-2) has an MFR (based on JIS K 7210, 190°C, 2.16 kgf load) of 0.5 g / 10 min and a density of 910 kg / m 3 is.

[0150] The following copolymers were used as the high-density polyethylene (C1) and the comparative high-density polyethylene (C1'): Polyethylene (C1-1): Hi-Zex 8200B (manufactured by Prime Polymer Co., Ltd.) The polyethylene (C1-1) had an MFR (based on JIS K 7210, 190°C, 2.16 kgf load) of 0.03 g / 10 min and a density of 952 kg / m 3 Polyethylene (C1'-1): Hi-Zex 5000S (manufactured by Prime Polymer Co., Ltd.) Polyethylene (C1'-1) has an MFR (based on JIS K 7210, 190°C, 2.16 kgf load) of 0.82 g / 10 min and a density of 949 kg / m 3 Polyethylene (C1'-2): Hi-Zex 2200J (manufactured by Prime Polymer Co., Ltd.) Polyethylene (C1'-2) has an MFR (JIS K 7210 compliant, 190°C, 2.16 kgf load) of 5.20 g / 10 min and a density of 964 kg / m 3 is.

[0151] The following copolymers were used as the ultra-high molecular weight polyethylene (C2) and the comparative ultra-high molecular weight polyethylene (C2'): Polyethylene (C2-1): Mipelon XM-220 (manufactured by Mitsui Chemicals, Inc.) The polyethylene (C2-1) had an intrinsic viscosity [η] of 28.0 dl / g and an average particle diameter D 50 is 30 μm, density is 938 kg / m 3 Polyethylene (C2'-1): Mipelon PM-200 (manufactured by Mitsui Chemicals, Inc.) Polyethylene (C2'-1) has an average particle diameter D 50 is 10 μm, density is 938 kg / m 3 Polyethylene (C2'-2): Mipelon XM-330 (manufactured by Mitsui Chemicals, Inc.) Polyethylene (C2'-2) has a weight average molecular weight of 2,000,000, an intrinsic viscosity [η] measured in decalin at 135°C of 28.5 dl / g, and an average particle diameter D 50 is 65 μm, density is 938 kg / m 3 is.

[0152] The following silicone master batches or silicone oils were used as the silicone compound (D). Compound (D-1): MB50-001 (manufactured by Dow Corning Toray Co., Ltd.) Compound (D-1) is a silicone master batch, and is a pellet in which a silicone gum having a kinematic viscosity of 1,000,000 cSt at 25°C is dispersed in polypropylene (the component (B3)), and the silicone gum content is 50 mass%. Compound (D-2): KF96-60,000 CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Compound (D-2) is a silicone oil having a kinematic viscosity of 60,000 cSt at 25°C. Compound (D-3): KF96-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd.) Compound (D-3) is a silicone oil having a kinematic viscosity of 3,000 cSt at 25°C.

[0153] The following masterbatches of phenolic resin-based crosslinking agents or organic peroxide-based crosslinking agents were used as crosslinking agents. Phenolic resin-based crosslinking agent masterbatch (CL-1): a mixture of a phenolic resin-based crosslinking agent (SP-1055, manufactured by Schenectady Chemicals, Inc.) and zinc oxide (mass ratio = 10:1). Organic peroxide-based crosslinking agent masterbatch (CL-2): a mixture of an organic peroxide-based crosslinking agent (Perhexa 25B, manufactured by NOF Corporation), divinylbenzene (DVB810, manufactured by NS Styrene Monomer), and a softener (E-1) described below (mass ratio = 5:2:3).

[0154] As other components, the following additives were used. Softener (E-1): Diana Process PW-90 (paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) Colorant: F32387MM (carbon black masterbatch, manufactured by DIC Corporation, mass ratio (mass%): polyethylene (component (C3)) / carbon = 60 / 40) Antioxidant: AO-60 (phenolic antioxidant, manufactured by ADEKA Corporation) Ultraviolet absorber: Tinuvin 326FL (benzotriazole ultraviolet absorber, manufactured by BASF Japan Ltd.) Weathering stabilizer: Tinuvin 770 (hindered amine (HALS) weathering stabilizer, manufactured by BASF Japan Ltd.) Other additives: Alflow P10 (fatty acid amide, manufactured by NOF Corporation)

[0155] <Production of Thermoplastic Elastomer (EL)> [Production Example 1] 46.9% by mass of oil-extended rubber (α-1) (33.3% by mass as copolymer (A-1)), 11.7% by mass of homopolymer (B2-1), 8.4% by mass of homopolymer (B2-2), 2.95% by mass of a phenolic resin-based crosslinking agent masterbatch (CL-1) as a crosslinking agent, 0.07% by mass of an antioxidant, 0.07 parts by mass of an ultraviolet absorber, 0.03% by mass of a weathering stabilizer, 1.3% by mass of a carbon black masterbatch, and 28.5% by mass of a softener (E-1) were thoroughly mixed in a Henschel mixer and extrusion-kneaded under the conditions described below to produce a thermoplastic elastomer (EL1) in which at least a portion of the copolymer (A) was crosslinked with the phenolic resin-based crosslinking agent. The contents (mass %) of the components (A), (B2), and (E) relative to 100.0 mass % of the obtained thermoplastic elastomer are shown in Table 1 as composition ratios.

[0156] (Mixing conditions) Extruder: Model number KTX-46, manufactured by Kobe Steel, Ltd. Cylinder temperature: C1 to C2 120°C, C3 to C4 140°C, C5 to C14 200°C Die temperature: 200°C Screw rotation speed: 400 rpm Extrusion rate: 80 kg / h

[0157] [Production Examples 2 to 4] Thermoplastic elastomers (EL2) to (EL4) were obtained in the same manner as in Production Example 1, except that the types and amounts of each component in Production Example 1 were changed as shown in Table 1. Thermoplastic elastomers (EL2) and (EL3) are obtained by crosslinking at least a portion of copolymer (A) with a phenolic resin-based crosslinking agent, and thermoplastic elastomer (EL4) is obtained by crosslinking at least a portion of copolymer (A) with an organic peroxide-based crosslinking agent.

[0158]

[0159] <Preparation of Sliding Composition> [Example 1] 22.2 mass% of the thermoplastic elastomer (EL1) obtained in Preparation Example 1, 9.1 mass% of copolymer (B1-1), 9.1 mass% of homopolymer (B2-2), 31.6 mass% of polyethylene (C1-1), 10.6 mass% of polyethylene (C2-1), 8.5 mass% of silicone compound (D-1), 2.4 mass% of silicone compound (D-3), 0.05 mass% of antioxidant, 0.18 parts by mass of ultraviolet absorber, 0.05 mass% of weathering stabilizer, 4.5 mass% of carbon black masterbatch, and 1.82 mass% of fatty acid amide were thoroughly mixed in a Henschel mixer and extrusion-kneaded under the following conditions to obtain pellets of the sliding composition. The various physical properties of molded articles produced using the pellets of the resulting composition were evaluated according to the methods described above. The results are shown in Table 3. The content (mass %) of each of the components (A), (B1), (B2), (C1), (C2), (D), and (E) relative to 100.0 mass % of the obtained sliding composition is shown in Table 3 as a composition ratio.

[0160] (Mixing conditions) Extruder: Model number KTX-46, manufactured by Kobe Steel, Ltd. Cylinder temperature: C1 to C2 120°C, C3 to C4 140°C, C5 to C14 200°C Die temperature: 200°C Screw rotation speed: 400 rpm Extrusion rate: 80 kg / h

[0161] [Examples 2 to 8 and Comparative Examples 1 to 9] Pellets of the sliding composition were produced in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 2. The various physical properties of molded articles produced using the resulting pellets of the composition were evaluated according to the methods described above. The results are shown in Table 3.

[0162]

[0163]

Claims

1. 7.0% by mass or more of an ethylene-α-olefin-non-conjugated polyene copolymer (A), 6.0% by mass or more of a propylene random copolymer (B1) having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, 10.0% by mass or more of a propylene homopolymer (B2) having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, and a density of 940 to 970 kg / m 3 and 15.0 mass % or more of a high-density polyethylene (C1) having a melt flow rate of 0.1 g / 10 min or less measured at 190°C under a load of 2.16 kgf, and an intrinsic viscosity [η] measured in a decalin solvent at 135°C of 10 to 40 dl / g and an average particle diameter D 50 is 22 to 50 μm, and the density is 940 kg / m 3 and 5.0 to 8.0 mass % of a silicone compound (D) having a kinematic viscosity at 25°C of 3,000 to 1,000,000 cSt, wherein the total content of the components (A), (B1), (B2), (C1), (C2) and (D) is 100.0 mass % or less, and at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked with a phenolic resin-based crosslinking agent.

2. The sliding composition according to claim 1, further comprising 0.1 to 10.0 mass% of a softener (E), the total content of the components (A), (B1), (B2), (C1), (C2), (D) and (E) being 100.0 mass% or less, the weight average molecular weight of the ethylene-α-olefin-non-conjugated polyene copolymer (A) being 280,000 or more, the intrinsic viscosity [η] measured in decalin at 135°C being 3.4 dl / g or more, the content of the ethylene-derived structural units being 70 mass% or less when the total content of the ethylene-derived structural units and the α-olefin-derived structural units is 100 mass%, and the content of the non-conjugated polyene-derived structural units of all the structural units of the copolymer (A) being 6.0 mass% or less.

3. The sliding composition according to claim 1 or 2, which has a Shore D hardness of 30 to 60 after 5 seconds of measurement in accordance with ISO 7619.

4. The sliding composition according to claim 1 or 2, wherein the content of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is 7.0 to 10.0% by mass.

5. The sliding composition according to claim 1 or 2, wherein the total content of the propylene random copolymer (B1) and the propylene homopolymer (B2) is 20.0 mass % or more.

6. The content of the propylene random copolymer (B1) is 9.0 to 15.0 mass %, and the density of the propylene random copolymer (B1) is 900 to 920 kg / m 3 3. The sliding composition according to claim 1, wherein 7. The content of the propylene homopolymer (B2) is 10.0 to 18.0 mass%, and the density of the propylene homopolymer (B2) is 900 to 920 kg / m 3 3. The sliding composition according to claim 1, wherein 8. The sliding composition according to claim 1 or 2, wherein the mass ratio (B2) / (B1) of the propylene homopolymer (B2) to the propylene random copolymer (B1) is 1.0 to 3.

0.

9. The content of the ultra-high molecular weight polyethylene (C2) is 10.0 to 30.0 mass%, and the average particle diameter D 50 3. The sliding composition according to claim 1, wherein the particle size is 22 to 30 μm.

10. A molded article obtained by molding the sliding composition according to claim 1 or 2.

11. A glass run channel comprising the molded article according to claim 10.

12. A polymer having an ethylene-α-olefin-non-conjugated polyene copolymer (A) of 7.0% by mass or more, a propylene random copolymer (B1) of 6.0% by mass or more having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, a propylene homopolymer (B2) of 10.0% by mass or more having a melt flow rate of 0.1 to 4.0 g / 10 min measured at 190°C under a load of 2.16 kgf, and a density of 940 to 970 kg / m 3 and 15.0 mass % or more of a high-density polyethylene (C1) having a melt flow rate of 0.1 g / 10 min or less measured at 190°C under a load of 2.16 kgf, and an intrinsic viscosity [η] measured in a decalin solvent at 135°C of 10 to 40 dl / g and an average particle diameter D 50 is 22 to 50 μm, and the density is 940 kg / m 3 and 5.0 to 8.0 mass % of a silicone compound (D) having a kinematic viscosity at 25°C of 3,000 to 1,000,000 cSt, wherein the total content of the components (A), (B1), (B2), (C1), (C2) and (D) is 100.0 mass % or less, and a method for producing a sliding composition in which at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) is crosslinked, the method comprising the step of crosslinking at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) with a phenolic resin-based crosslinking agent.