A sliding composition and its uses, and a method for manufacturing the 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

[Technical Field]

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

[0002] Olefin-based thermoplastic elastomers are lightweight, easily recyclable, and do not produce toxic gases when incinerated. Therefore, they are widely used as substitutes for vulcanized rubber in automotive parts, industrial machinery parts, electrical and electronic components, and building materials, particularly from the perspectives of energy conservation, resource conservation, and, more recently, environmental protection. An example of such an automotive part is the glass run channel.

[0003] Glass run channels are sealing materials (guide members) installed between window glass and window frames, and because sliding properties with respect to the glass are required, conventional products include thermoplastic elastomer compositions containing fine particles made of silicone-based additives or polyethylene in a thermoplastic elastomer (in particular, compositions that have sliding properties are sometimes called "sliding compositions").

[0004] Patent Document 1 describes a configuration (Example 8) in which a glass sliding layer bonded to a glass run channel body includes 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 of a thermoplastic elastomer blended with a silylated polyolefin exhibits excellent adhesion between the substrate layer and the surface layer, as well as superior abrasion resistance.

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

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, when the inventors examined the extrusion moldability of an olefinic thermoplastic elastomer composition (sliding composition) containing fine particles composed of a silicone-based additive, polyethylene, etc., it was found that in a formulation containing a silicone-based additive, problems may occur in the adhesion of the corner portions, and that foreign matter called "meyani" adheres to the die of the molding machine, impairing the processability. It was also found that large irregularities occur on the surface of the molded product, impairing the appearance of the molded product. Furthermore, it was found that there is room for improvement in heat aging resistance and sliding characteristics.

[0009] One aspect of the present invention provides a sliding composition capable of manufacturing a molded body such as a glass run channel that achieves both sliding characteristics and adhesion at the corner portions, and is also excellent in the balance of extrusion moldability, appearance, heat aging resistance, etc., and a method for manufacturing the sliding composition.

Means for Solving the Problems

[0010] The configuration example of the present invention is as follows. [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-based random copolymer (B1) having a melt flow rate measured at 190°C and a load of 2.16 kgf of 0.l to 4.0 g / 10 min, A propylene homopolymer (B2) with a melt flow rate of 0.1 to 4.0 g / 10 min, measured at 190°C and a load of 2.16 kgf, is present in an amount of 10.0% by mass or more. Density of 940-970 kg / m³ 3 The mixture contains 15.0% by mass or more of high-density polyethylene (C1) with a melt flow rate of 0.1 g / 10 min or less, measured at 190°C and a load of 2.16 kgf. The intrinsic viscosity [η] measured in decalin solvent at 135°C was 10-40 dl / g, and the average particle size D 50 The particle size is 22-50 μm, and the density is 940 kg / m³. 3 Ultra-high molecular weight polyethylene (C2) less than 10.0% by mass and It contains 5.0 to 8.0% by mass of a silicone compound (D) having a kinematic viscosity of 3,000 to 1,000,000 cSt at 25°C (however, the total content of the aforementioned components (A), (B1), (B2), (C1), (C2), and (D) is 100.0% by mass or less). A sliding composition comprising at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) crosslinked with a phenolic resin-based crosslinking agent.

[0011] [2] Furthermore, it contains 0.1 to 10.0% by mass of a softening agent (E) (however, the total content of the aforementioned components (A), (B1), (B2), (C1), (C2), (D), and (E) is 100.0% by mass or less). The sliding composition according to [1], 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 is 3.4 dl / g or more, the content of ethylene-derived constituent units is 70% by mass or less (provided that the total content of ethylene-derived constituent units and α-olefin-derived constituent units is 100% by mass), and the content of non-conjugated polyene-derived constituent units in the total constituent units of copolymer (A) is 6.0% by mass or less.

[0012] [3] A sliding composition according to [1] or [2], wherein the Shore D hardness (after 5 seconds) measured in accordance with ISO 7619 is 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% by mass.

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

[0015] [6] The content of the propylene-based random copolymer (B1) is 9.0 to 15.0% by mass, and the density of the propylene-based random copolymer (B1) is 900 to 920 kg / m³. 3 The sliding composition described in any of [1] to [5].

[0016] [7] The content of the propylene homopolymer (B2) is 10.0 to 18.0% by mass, and the density of the propylene homopolymer (B2) is 900 to 920 kg / m³. 3 The sliding composition described in any of [1] to [6].

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

[0018] [9] The content of the aforementioned ultra-high molecular weight polyethylene (C2) is 10.0 to 30.0% by mass, and the average particle size D 50 A sliding composition according to any one of [1] to [8], wherein the diameter 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 including the molded article according to

[10] .

[0021]

[12] 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 measured at 190 °C and 2.16 kgf load of 0.1 to 4.0 g / 10 min, 10.0% by mass or more of a propylene homopolymer (B2) having a melt flow rate measured at 190 °C and 2.16 kgf load of 0.1 to 4.0 g / 10 min, a density of 940 to 970 kg / m 3 15.0% by mass or more of a high-density polyethylene (C1) having a melt flow rate measured at 190 °C and 2.16 kgf load of 0.1 g / 10 min or less, an intrinsic viscosity [η] measured in a decalin solvent at 135 °C of 10 to 40 dl / g, an average particle diameter D 50 of 22 to 50 μm, and a density of less than 940 kg / m 3 10.0% by mass or more of an ultra-high molecular weight polyethylene (C2), and containing 5.0 to 8.0% by mass of a silicone compound (D) having a kinematic viscosity at 25 °C of 3000 to 1,000,000 cSt (however, the total content of the components (A), (B1), (B2), (C1), (C2) and (D) is 100.0% by mass or less). A method for producing a sliding composition in which at least a part of the ethylene·α-olefin·non-conjugated polyene copolymer (A) is crosslinked, The method for producing a sliding composition includes a step of crosslinking at least a part of the ethylene·α-olefin·non-conjugated polyene copolymer (A) with a phenolic resin crosslinking agent.

Advantages of the Invention

[0022] According to one embodiment of the present invention, a sliding composition can be obtained that achieves both sliding properties and adhesion at corners, and also provides an excellent balance of extrudeability, appearance, and heat aging resistance, such as a glass run channel. [Modes for carrying out the invention]

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

[0024] <<Sliding Composition>> A sliding composition according to one aspect of the present invention (hereinafter also simply referred to as "this composition") is Ethylene-α-olefin-non-conjugated polyene copolymer (A), A propylene-based random copolymer (B1) with a melt flow rate (MFR) of 0.1 to 4.0 g / 10 min measured at 190°C and a load of 2.16 kgf, A propylene homopolymer (B2) with an MFR of 0.1 to 4.0 g / 10 min measured at 190°C and a load of 2.16 kgf, Density of 940-970 kg / m³ 3 High-density polyethylene (C1) is such that the MFR measured at 190°C and a load of 2.16 kgf is 0.1 g / 10 min or less. The intrinsic viscosity [η] measured in decalin solvent at 135°C was 10-40 dl / g, and the average particle size D 50 The particle size is 22-50 μm, and the density is 940 kg / m³. 3 Ultra-high molecular weight polyethylene (C2) less than, and It contains a silicone compound (D) having a kinematic viscosity of 3,000 to 1,000,000 cSt at 25°C. Furthermore, this composition is characterized in that at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) is crosslinked with a phenol resin-based crosslinking agent.

[0025] The content of component (A) in this 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 this composition.

[0026] The content of component (B1) in this 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 this composition. The content of component (B2) in this 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 this composition. Here, the total content of component (B1) and component (B2) is preferably 20.0% by mass or more, more preferably 20.0 to 25.0% by mass, relative to 100.0% by mass of the composition. B1 ) components ( B2 The mass ratio [(B2) / (B1)] of ) is preferably 1.0 to 3.0, more preferably 1.2 to 2.8.

[0027] The content of component (C1) in this 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 this composition. The content of component (C2) in this 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. Here, the total content of component (C1) and component (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. C1 ) components ( C2The mass ratio [(C2) / (C1)] of ) is preferably 0.1 to 1.0, and more preferably 0.2 to 0.7.

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

[0029] By incorporating (containing) components (A), (B1), (B2), (C1), (C2), and (D) in the aforementioned proportions, this composition can produce a molded article that achieves both sliding properties and corner adhesion, while also exhibiting an excellent balance of extrudeability, appearance, and heat aging resistance.

[0030] If the amount of ethylene-α-olefin-non-conjugated polyene copolymer (A) is below the lower limit, it lacks flexibility and creases, while if it exceeds the upper limit, the sliding properties tend to deteriorate. If the amount of each component of the propylene resin (B) is below the lower limit, the moldability deteriorates, while if it exceeds the upper limit, it tends to lack flexibility and develop creases. If the amount of high-density polyethylene (C1) blended is below the lower limit, the sliding properties deteriorate, while if it exceeds the upper limit, it tends to harden and develop creases. If the amount of ultra-high molecular weight polyethylene (C2) blended is below the lower limit, the elongation decreases and the low-temperature properties deteriorate. On the other hand, if it exceeds the upper limit, it tends to soften and the sliding properties deteriorate. If the amount of silicone compound (D) is below the lower limit, the sliding properties deteriorate, while if it exceeds the upper limit, the adhesion of the corners of the resulting molded article decreases, and the low-temperature impact strength also tends to deteriorate. The following provides a detailed explanation of each component.

[0031] [Ethylene-α-olefin-nonconjugated polyene copolymer (A)] Ethylene-α-olefin-non-conjugated polyene copolymer (A) is a copolymer containing constituent units derived from ethylene, α-olefins other than ethylene, and non-conjugated polyenes. This composition may contain only one copolymer (A), or it may contain two or more copolymers.

[0032] The α-olefins are typically α-olefins having 3 to 20 carbon atoms. 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 individually or in combination of two or more types.

[0033] The aforementioned non-conjugated polyenes include, specifically, chain-like 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, and 5-isopropylidene-2-norbornene. Examples 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, α-olefins other than ethylene, and unconjugated polyenes) may consist solely of monomers obtained from biomass-derived raw materials, or solely of monomers obtained from fossil fuel-derived raw materials, and biomass-derived Coming A mixture of monomers obtained from raw materials and monomers obtained from fossil fuel-derived raw materials may also be used.

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

[0036] In copolymer (A), the content of structural units derived from α-olefins having 3 to 20 carbon atoms 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 sum of the content of structural units derived from ethylene and structural units derived from α-olefins having 3 to 20 carbon atoms is taken as 100% by mass. Furthermore, when the sum of the content of structural units derived from ethylene and structural units derived from α-olefins having 3 to 20 carbon atoms is taken as 100 mol%, the content of structural units derived from α-olefins having 3 to 20 carbon atoms is preferably 20 to 40 mol%, and more preferably 20 to 30 mol%.

[0037] When the content of ethylene-derived structural units and the content of α-olefin-derived structural units having 3 to 20 carbon atoms are within the aforementioned ranges, a sliding composition with excellent mechanical properties, rubber elasticity, cold resistance, and processability tends to be obtained. When the content of ethylene-derived structural units is 70% by mass or less and the content of α-olefin-derived structural units having 3 to 20 carbon atoms is 30% by mass or more, the sliding composition tends to have excellent flexibility, rubber elasticity at low temperatures, and processability. When the content of ethylene-derived structural units is 55% by mass or more and the content of α-olefin-derived structural units having 3 to 20 carbon atoms is 45% by mass or less, the 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% by mass or less, more preferably 2.0 to 6.0% by mass, and even more preferably 3.0 to 6.0% by mass. When the content of non-conjugated polyene-derived structural units is within the above range, molded product It tends to have excellent appearance and heat aging resistance. The content of each structural unit in copolymer (A) is: 13 It can be measured by 13C-NMR, and for example, peak identification and quantification can be performed according to the method described later and the method described in "Handbook of Polymer Analysis" (Asakura Shoten, 2008, 1st edition, pp. 184-211).

[0039] Copolymer (A) has an intrinsic viscosity [η] measured in decalin at 135°C, preferably 3.4 dl / g or higher, 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 the above range, a sliding composition with 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 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 falls below the lower limit, the crosslinking efficiency in the thermoplastic elastomer described later may decrease, and the rubber elasticity may decrease. If the iodine value exceeds the upper limit, the crosslinking density may become too high, reducing elongation and worsening the balance of physical properties.

[0041] The weight-average molecular weight (Mw) of copolymer (A), as measured by GPC, is preferably 280,000 or more, and more preferably 280,000 to 500,000. The molecular weight distribution (Mw / Mn) is usually 1.5 to 50, preferably 1.8 to 30, and more preferably 2.0 to 6. If the molecular weight distribution falls below the above range, the content of low molecular weight components decreases, which may reduce processability. If the molecular weight distribution exceeds the above range, the content of low molecular weight components increases, which may worsen fogging resistance.

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

[0043] The copolymer (A) may be a commercially available product or may be manufactured by a conventionally known method. Conventionally known methods include those described in "Polymer Manufacturing Process" (Kogyo Chosakai Co., Ltd., pp. 309-330) or in Japanese Patent Publication Nos. 9-71617, 9-71618, 9-208615, 10-67823, 10-67824, 10-110054, International Publication Nos. 2009 / 081792 and 2009 / 081794, etc., related to the applicant of the present application.

[0044] Examples of olefin polymerization catalysts that are preferably used in the production of the copolymer (A) include: A known Ziegler catalyst consisting of a transition metal compound such as vanadium (V), zirconium (Zr), or titanium (Ti), and an organoaluminum compound (organoaluminum oxy compound); A known metallocene catalyst consisting of a metallocene compound of a transition metal selected from Group 4 of the periodic table of elements and an organoaluminum oxy compound or an ionized ionic compound (for example, the metallocene catalyst described in Japanese Patent Publication No. 9-40586); Known metallocene catalysts comprising a specific transition metal compound and a co-catalyst such as a boron compound (for example, metallocene catalysts described in International Publication No. 2009 / 072553); Examples of transition metal catalysts include those 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 (for example, the transition metal catalyst described in Japanese Patent Application Publication No. 2011-52231). In particular, using a metallocene catalyst is preferable because it allows for a uniform distribution of unconjugated polyenes, enabling high crosslinking efficiency even with a small amount of unconjugated polyene introduction, and also because it has high catalytic activity and can reduce the chlorine content derived from the catalyst.

[0045] Furthermore, the copolymer (A) may be used as a component (α) containing the copolymer (A), such as a copolymer (hereinafter also referred to as "oil-expanded rubber") obtained by pre-mixing the copolymer (A) with a petroleum-based plasticizer (softener) and oil-expanding it, before mixing it with other components described later. Examples of the petroleum-based plasticizer include plasticizers similar to the "petroleum-based plasticizer" exemplified in the softener (E) of [Other Components] described later.

[0046] Conventional known methods can be used as the method for producing the oil-expanded rubber (oil-expanding method). For example, a method of mechanically kneading the copolymer (A) and petroleum-based plasticizer using a mixing roll or Banbury mixer and then oil-expanding the material can be used. Another method involves adding a predetermined amount of petroleum-based plasticizer to the copolymer (A) and then removing the solvent by methods such as steam stripping. A third method involves stirring a mixture of crumb-like copolymer (A) and petroleum-based plasticizer in a Henschel mixer or the like to impregnate the material.

[0047] The aforementioned oil-spreading rubber may be a commercially available product, such as Mitsui EPT manufactured by Mitsui Chemicals, Inc., JSR EPR manufactured by JSR Corporation, Esprene® manufactured by Sumitomo Chemical Co., Ltd., Keltan® manufactured by LANXESS Corporation, KEP® manufactured by KUMHO POLYCHEM Co., Ltd., and NODEL® manufactured by DOW CHEMICAL Corporation.

[0048] [Propylene resin (B)] This 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 α-olefin (propylene·α-olefin copolymer) and is a random copolymer. This composition may contain only one copolymer (B1) and one polymer (B2), or it may contain two or more of each.

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

[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%. Here, the sum of the content of propylene-derived constituent units and the content of α-olefin-derived constituent units is 100 mol%.

[0051] Furthermore, the propylene-α-olefin copolymer may also contain small amounts of ethylene and other olefin-derived constituent units with carbon atoms other than 3 to 12 (e.g., 10 mol% or less relative to the total constituent units of the propylene copolymer (A)). The other olefin may be used individually or in combination of two or more types.

[0052] The melt flow rate (MFR) of copolymer (B1), measured at 190°C and a load of 2.16 kgf in accordance with JIS K 7210, was 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 copolymer (B1) is within the aforementioned range, the composition is easy to injection mold, and a molded article with a good balance of dimensional stability and impact strength can be easily obtained.

[0053] The density of copolymer (B1) according to JIS K 7112 Method B (pycnometer method) is preferably 900-920 kg / cm³. 3 More preferably 910-920 kg / cm² 3 That is the case. When the density of the copolymer (B1) is within the aforementioned range, the composition is easy to injection mold, and a molded article with a good balance of dimensional stability and impact strength can be easily obtained.

[0054] <Propylene homopolymer (B2)> According to JIS K7210 for polymer (B2), the melt flow rate (MFR), measured at 190°C and a load of 2.16 kgf, was 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 polymer (B2) is within the aforementioned range, the composition is easy to injection mold, and a molded article with a good balance of dimensional stability and impact strength can be easily obtained.

[0055] The density of polymer (B2), measured according to JIS K7112 Method B (pycnometer method), is preferably 900-920 kg / cm³. 3 More preferably 910-920 kg / cm² 3 That is the case. When the density of polymer (B2) is within the aforementioned range, the composition is easy to injection mold, and a molded article with a good balance of dimensional stability and impact strength can be easily obtained.

[0056] The copolymer (B1) and polymer (B2) may be commercially available products or may be manufactured as appropriate by known methods. The monomers constituting the copolymer (B1) and / or polymer (B2) (e.g., propylene, α-olefins other than propylene) may consist solely of monomers obtained from biomass-derived raw materials, or solely of monomers obtained from fossil fuel-derived raw materials, and may consist solely of monomers obtained from biomass-derived raw materials. Coming A mixture of monomers obtained from raw materials and monomers obtained from fossil fuel-derived raw materials may also be used.

[0057] This composition may also contain a propylene-based polymer (B3) other than copolymer (B1) and polymer (B2), to the extent that it 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) is an example.

[0058] Examples of commercially available propylene resins (B) include Prime PolyPro® manufactured by Prime Polymer Co., Ltd., Novatec manufactured by Nippon Polypropylene Co., Ltd., and Sumitomo® Noblen® manufactured by Sumitomo Chemical Co., Ltd.

[0059] [Ethylene resin (C)] This composition contains high-density polyethylene (C1) and ultra-high molecular weight polyethylene (C2) as ethylene-based resins (C). High-density polyethylene (C1) is a component that provides both adhesiveness and sliding properties, while ultra-high molecular weight polyethylene (C2) is a component that provides both extrudeability and sliding properties. This composition may contain only one type of high-density polyethylene (C1) and one type of ultra-high molecular weight polyethylene (C2), or it may contain two or more types.

[0060] <High-density polyethylene (C1)> Examples of high-density polyethylene (C1) include ethylene homopolymers and ethylene-α-olefin copolymers. Specific examples of α-olefins 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. The α-olefin may be used individually or in combination of two or more types.

[0061] When the high-density polyethylene (C1) is an ethylene-α-olefin copolymer, the content of ethylene-derived constituent 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 constituent 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 constituent units and the content of α-olefin-derived constituent units is 100 mol%.

[0062] The density of high-density polyethylene (C1), measured according to JIS K7112 Method B (pycnometer method), is 940-970 kg / cm³. 3 Preferably 945-965 kg / cm² 3 That is the case. When the density of high-density polyethylene (C1) is within the aforementioned range, a molded article with excellent adhesive properties can be easily obtained.

[0063] The melting point of high-density polyethylene (C1), as 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 adhesion. Here, the melting point is the crystal melting peak temperature (Tm) determined from the thermogram measured when approximately 10 mg of the sample is heated from -40°C to 200°C at a heating rate of 10°C / min using a differential scanning calorimeter, held at 200°C for 1 minute, cooled down 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] According to JIS K 7210 for high-density polyethylene (C1), the MFR measured at 190°C and 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.

[0065] Polymerization catalysts used in the production of high-density polyethylene (C1) include, for example, well-known multi-site catalysts such as Ziegler and Phillips catalysts, Kaminsky catalysts such as zirconocene, titanocene, and hafnocene (collectively referred to as metallocenes), and highly active single-site catalysts such as post-metallocene catalysts. High-density polyethylene (C1) can be produced by known polymerization methods using these polymerization catalysts.

[0066] <Ultra-high molecular weight polyethylene (C2)> Examples of ultra-high molecular weight polyethylene (C2) include ethylene homopolymers and ethylene-α-olefin copolymers. Specific examples of α-olefins 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. The α-olefin may be used individually or in combination of two or more types.

[0067] When the ultra-high molecular weight polyethylene (C2) is an ethylene-α-olefin copolymer, the content of ethylene-derived constituent 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 constituent 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 constituent units and the content of α-olefin-derived constituent units is 100 mol%.

[0068] The intrinsic viscosity [η] of 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 size D of ultra-high molecular weight polyethylene (C2) 50 The particle size is 22-50 μm, more preferably 22-40 μm, and even more preferably 22-30 μm. The average particle size is measured by the method described in the examples below. When the average particle size of ultra-high molecular weight polyethylene (C2) is within the above range, a molded article with excellent extrusion moldability can be easily obtained. The average particle diameter D 50 This is measured by the method described in the examples below.

[0070] The density of ultra-high molecular weight polyethylene (C2), measured according to JIS K7112 Method B (pycnometer method), was 940 kg / cm³. 3 Less than 850-930 kg / cm³ 3 More preferably 850-920 kg / cm² 3 That is the case. When the density of ultra-high molecular weight polyethylene (C2) is within the aforementioned range, a molded article with excellent extrusion moldability can be easily obtained.

[0071] As a method for producing ultra-high molecular weight polyethylene (C2), known polymerization methods using olefin polymerization catalysts are used. For example, it is preferable to produce it by solution polymerization, slurry polymerization, high-pressure ionic polymerization, gas-phase polymerization, or bulk polymerization and solution polymerization using complex catalysts such as Ziegler-Natta catalysts, metallocene complexes, or non-metallocene complexes. Among these, it is particularly preferable to use a method of polymerizing monomers using Ziegler-Natta catalysts or complex catalysts, or a method of polymerizing monomers in the presence of a metallocene catalyst.

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

[0073] This composition may also contain ethylene polymers (C3) other than high-density polyethylene (C1) and ultra-high molecular weight polyethylene (C2), to the extent that they do not impair the effects of the present invention. Examples of commercially available ethylene-based resins (C) include Hyzex (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., Evolu (registered trademark) manufactured by Prime Polymer Co., Ltd., and Suntech manufactured by Asahi Kasei Corporation.

[0074] [Silicone compound (D)] This composition contains silicone compound (D). Silicone compound (D) is primarily added to reduce sliding resistance. This composition may contain only one type of silicone compound (D), or it may contain two or more types.

[0075] The kinematic viscosity of 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, from the viewpoint of reducing sliding resistance. When using multiple types of silicone compound (D), it is sufficient that the kinematic viscosity of each at 25°C falls 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, and (D-1) silicone oil, preferably with a kinematic viscosity of 5000 mm². 2 It is preferable to use a silicone oil with a viscosity of less than / s in combination with (D-2) silicone gum.

[0077] When (D-1) silicone oil and (D-2) silicone gum are used in combination, the mass mixing 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 is preferably one with 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. Furthermore, the silicone gum is preferably non-crosslinked. The weight-average molecular weight can be measured, for example, by GPC (gel permeation chromatography).

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

[0081] Furthermore, GPC measurement of silicone gum in a masterbatch can be performed by first separating the silicone gum from the polypropylene by performing the following treatment on the masterbatch, and then measuring the resulting silicone gum.

[0082] (Separation process between silicone gum and polypropylene) First, weigh 0.05 g of the sample (masterbatch), add 10 mL of xylene containing 0.1 g / L BHT (dibutylhydroxytoluene), and stir at 125°C for 60 minutes to dissolve the masterbatch. After visually confirming that the masterbatch is completely dissolved, allow the solution to stand at room temperature for about 3 hours to precipitate crystalline polypropylene in the solution. Filter the solution containing these precipitated crystals using a Sumitomo Electric Fluoropore FP-100 (1 μm) via suction filtration, wash with 3 mL of xylene to separate CXS (xylene-soluble portion, silicone gum) and CXIS (xylene-insoluble portion, polypropylene). Pre-dry the CXS by nitrogen blowing at room temperature, then vacuum dry at 60°C. Vacuum drying is continued until no further weight loss is observed. GPC measurement is performed using the CXS portion after vacuum drying.

[0083] [Other ingredients] This composition may, if necessary, contain other components other than those described above (A) to (D), as long as they do not impair the effects of the present invention. Other components include, for example, other resins and elastomers other than those mentioned above (A) to (C), softeners (E), heat stabilizers, antistatic agents, weather stabilizers, antioxidants, UV absorbers, light stabilizers, fillers, flame retardants, colorants, and lubricants. Each of these other components may be used individually or in combination of two or more.

[0084] <Softener (E)> As the softening agent (E), a softening agent (plasticizer) commonly used in rubber can be used. The softening agent (E) may be a softening agent obtained from fossil fuel-derived raw materials, or a softening agent obtained from animal or plant-derived raw materials.

[0085] Specific examples of plasticizers (E) include: petroleum-based plasticizers such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; 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; sub(factis); 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 its derivatives; synthetic polymers 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, and modified liquid poly butadiene Examples include liquid thiocol and hydrocarbon-based synthetic lubricants. Among these, petroleum-based plasticizers, particularly process oils, such as paraffinic process oils and naphthenic process oils, are preferred.

[0086] When a softening agent (E) is added to this composition, the amount (content) of the softening agent is preferably 0.1 to 10.0% by mass, more preferably 1.0 to 9.8% by mass, based on 100.0% by mass of the composition, from the viewpoint of suppressing bleeding and improving paint adhesion. However, the total content of the components (A), (B1), (B2), (C1), (C2), (D), and (E) is 100.0% by mass or less. Furthermore, when the aforementioned oil-expandable rubber is used as a raw material for this composition, the petroleum-based plasticizer used in the oil-expanding process is included in the softener (E).

[0087] <<Method for producing this composition>> This composition can be produced by melt-kneading, followed by granulation or grinding, of an ethylene-α-olefin-non-conjugated polyene copolymer (A), a propylene-based random copolymer (B1), a propylene homopolymer (B2), high-density polyethylene (C1), ultra-high molecular weight polyethylene (C2), a silicone compound (D), and, if necessary, other components.

[0088] This 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 this composition includes a step of crosslinking at least a portion of the copolymer (A) with a phenolic resin-based crosslinking agent. The above step is not particularly limited as long as it is a conventionally known crosslinking method using a phenolic resin-based crosslinking agent, but it is preferable to follow the method described below in terms of sliding properties, low-temperature properties and flexibility. A method for producing a thermoplastic elastomer (hereinafter also simply referred to as "thermoplastic elastomer") in which at least a portion of copolymer (A) is partially or completely crosslinked with the phenolic resin crosslinking agent by dynamically heat-treating a mixture containing copolymer (A), a phenolic resin crosslinking agent, preferably a portion of propylene resin (B), and other components as needed, and then melt-kneading the remaining propylene resin (B), high-density polyethylene (C1), ultra-high molecular weight polyethylene (C2), a silicone compound (D), and other components as needed, followed by granulation or pulverization.

[0089] The aforementioned kneading can be carried out using a kneading device, which may include a mixing roll, an intensive mixer (e.g., a Banbury mixer, a kneader), a single-screw or twin-screw extruder, etc., but a closed-type device is preferred. The granulation or grinding may be carried out by conventionally known methods.

[0090] [Thermoplastic elastomer] As a raw material for this composition, a thermoplastic elastomer may be used in which at least a portion of the ethylene-α-olefin-non-conjugated polyene copolymer (A), which has been prepared in advance as described above, 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 (1) or (2) below. (1) A partially or completely crosslinked thermoplastic elastomer obtained by dynamically heat-treating a mixture containing (a) crosslinked olefin copolymer rubber (uncrosslinked rubber) (e.g., copolymer (A)) [hereinafter also referred to as "component (a)"], (b) crystalline polypropylene (e.g., propylene resin (B)) [hereinafter also referred to as "component (b)"], and optionally (c) petroleum-based plasticizer [hereinafter also referred to as "component (c)"] in the presence of a phenolic resin crosslinking agent; (2) A partially or completely crosslinked thermoplastic elastomer is obtained by dynamically heat-treating a mixture containing component (a), a portion of component (b), and optionally component (c) in the presence of a phenolic resin crosslinking agent to obtain a crosslinked rubber composition, to which (d) the remaining component (b) is uniformly blended.

[0092] The aforementioned (c) petroleum-based plasticizer is a high-boiling-point petroleum fraction that is typically used when rolling rubber to weaken the intermolecular forces of the rubber, thereby facilitating processing, and to aid in the dispersion of optionally included carbon black, white carbon, etc., or to reduce the hardness of vulcanized rubber and increase its flexibility and elasticity. Component (c) may include plasticizers similar to those described in [Other Components] above.

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

[0094] Furthermore, component (a) may be a combination of copolymer (A) and 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, based on 100 parts by mass of the total amount of component (b) and component (a). Examples of other uncrosslinked rubbers include diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), and butyl rubber (IIR), as well as SEBS and polyisobutylene.

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

[0096] A more specific example of the thermoplastic elastomer is a thermoplastic elastomer 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) (provided that 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 crosslinking agent, wherein the uncrosslinked rubber (a-1) is partially crosslinked.

[0097] The phenolic resin-based crosslinking agent is heat hardening It is a curable resin, also known as a phenolic resin-based curing resin or phenolic resin. Examples of phenolic resin-based crosslinking agents include halogenated phenolic resin-based crosslinking agents. By using the aforementioned phenolic resin-based crosslinking agent, a sliding composition with excellent heat aging resistance can be obtained.

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

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

[0100] Examples of phenolic resin crosslinking agents include compounds represented by the following formula (I) or compounds obtained by substituting the terminal hydroxyl group (-CH2-OH) of the compound represented by the following formula (I) with a halogen atom.

[0101] [ka] (In the formula, Q is -CH2- or -CH2-O-CH2-, m is an integer between 0 and 20, and R' is an organic group.)

[0102] Preferably, Q is -CH2-O-CH2-, 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] Examples of compounds represented by formula (I) or compounds in which the terminal hydroxyl group (-CH2-OH) of the compound represented by formula (I) is substituted with a halogen atom include alkylphenol formaldehyde resin, methylolated alkylphenol resin, halogenated alkylphenol resin, and the like. Halogenated alkylphenol resin is preferred, and more preferably, a brominated compound in which the terminal hydroxyl group (-CH2-OH) of the compound represented by formula (I) is substituted with a bromine atom. An example of such a brominated compound is shown in formula (II) below.

[0104] [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.)

[0105] Examples of the phenolic resin-based crosslinking agents include Takkirol 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.) and Takkirol 250-I (bromine). Contains4% brominated alkylphenol formaldehyde resin (manufactured by Taoka Chemical Industry Co., Ltd.), Tackirol 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), 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 (Anchor Examples include Schenectady SP1059 (manufactured by Schenectady Chem.), Symphorm-C-1001 (manufactured by Anchor Chem.), Tamanol 531 (manufactured by Arakawa Chemical Industries, Ltd.), Schenectady SP1059 (manufactured by Schenectady Chem.), Schenectady SP1045 (manufactured by Schenectady Chem.), CRR-0803 (manufactured by UCC), 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 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 aforementioned phenolic resin-based crosslinking agent include the techniques described in U.S. Patent No. 4,311,628, U.S. Patent No. 2,972,600, and U.S. Patent No. 3,287,440, among others.

[0107] U.S. Patent No. 4,311,628 discloses a phenolic curative system comprising a phenolic curing resin and a cure activator. The basic component of this system is a phenolic resin crosslinking agent produced by 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 condensation of difunctional phenol dialcohols (preferably dimethylolphenols with the para position substituted with a C5-C10 alkyl group). 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 curing 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 halogen donors, preferably with hydrogen halide scavengers. While halogenated phenolic resin crosslinking agents, preferably those containing 2-10% by mass of bromine, do not typically require halogen donors, they are used simultaneously with hydrogen halide scavengers such as metal oxides, preferably zinc oxide, selected from, for example, iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide, and zinc oxide. These hydrogen halide scavengers, such as zinc oxide, are typically used in amounts of 1-20 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; however, in the case of rubbers that are not easily crosslinked by the phenolic resin crosslinking agent, it is desirable to use both a halogen donor and zinc oxide.Methods for producing halogenated phenolic curable resins and their use in crosslinking agent systems using zinc oxide are described in U.S. Patent Nos. 2,972,600 and 3,093,613, respectively, and their disclosures, along with those of U.S. Patent Nos. 3,287,440 and 3,709,840, are incorporated herein by reference. Examples of suitable halogen donors include halogen-donating polymers such as stannous chloride, ferric chloride, chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and polychlorobutadiene (neoprene rubber). For further details on phenolic vulcanizing agent systems, see "Vulcanization and Vulcanizing Agents" (W. Hoffman, Palmerton Publishing Company). Suitable phenolic resin crosslinking agents are commercially available; for example, such crosslinking agents can be purchased from Schenectady Chemicals, Inc. under the trade names "SP1045," "CRJ352," "SP1055," and "SP1056."

[0108] The phenolic resin crosslinking agent is used in an amount preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of component (a). The phenolic resin crosslinking agent may also be used in the form of a crosslinking agent masterbatch that has been pre-mixed with a hydrogen halide scavenger such as zinc oxide. By adjusting the amount of phenolic resin-based crosslinking agent within the aforementioned 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 phenol resin-based crosslinking agent, crosslinking aids such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N,4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and trimethylolpropane-N,N'-m-phenylenedimaleimide may be used; and polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate, as well as polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate may also be used.

[0110] By using the aforementioned auxiliary agent, a uniform and gentle crosslinking reaction can be expected. Divinylbenzene is preferred as the auxiliary agent. Divinylbenzene is easy to handle, has good compatibility with the uncrosslinked rubber (a-1) and crystalline polyolefin (b-1), and has the effect of solubilizing the phenolic resin crosslinking agent. It also acts as a dispersant for the phenolic resin crosslinking agent, resulting in a homogeneous crosslinking effect by heat treatment, and making it possible to easily obtain a thermoplastic elastomer with a good balance of fluidity and physical properties.

[0111] The crosslinking aid or aid 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 component (a).

[0112] Furthermore, when dynamic crosslinking is performed using the phenolic resin-based crosslinking agent, the phenolic resin-based crosslinking agent dispersion To facilitate this process, a dispersion enhancer may be used. Applicable dispersion Examples of 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), etc.

[0113] The amount of the dispersion promoter used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total of components (a) and (b). When the amount of dispersion accelerator used is within the aforementioned range, the crosslinking reaction does not proceed too quickly, and the dispersion accelerator is less likely to remain unreacted in the resulting thermoplastic elastomer. This makes it possible to easily obtain a thermoplastic elastomer with excellent fluidity and less susceptibility to changes in physical properties due to thermal history during processing and molding.

[0114] The term "dynamically heat-treating" refers to kneading each of the aforementioned components in a molten state. The aforementioned kneading can be carried out using a kneading device, and conventionally known kneading devices such as open-type mixing rolls, closed-type Banbury mixers, extruders, kneaders, and continuous mixers can be used as the kneading device. Among these, closed-type kneading devices are preferred. The aforementioned kneading is preferably carried out under an atmosphere of an inert gas such as nitrogen gas or carbon dioxide.

[0115] The mixing temperature is usually 150-280°C, preferably 170-250°C, and the mixing time is usually 0.5-20 minutes, preferably 1-10 minutes. Furthermore, it is preferable to perform the kneading while applying shear force, with the applied shear force being a shear rate of 10 to 50,000 sec. -1 Preferably 100 to 20,000 seconds -1 It is desirable to keep it within that range.

[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 article with excellent rigidity.

[0117] The MFR of the thermoplastic elastomer, measured in accordance with ASTM D1238 at 230°C and a load of 10 kgf, is typically 0.1 to 100 g / 10 min, preferably 1 to 100 g / 10 min. When the MFR is above the lower limit, the fluidity is good and molding in the extruder becomes easy. When the MFR is below the upper limit, the occurrence of drawdown and other issues when discharged from the extruder die can be suppressed, resulting in good extruderability.

[0118] <<Molded body>> A molded article according to one aspect of the present invention (hereinafter also referred to as "the molded article") is a molded article obtained by molding the composition. This molded product can be manufactured using various known molding methods, specifically extrusion molding, press molding, injection molding, calendering, and hollow molding. etc. This composition can be manufactured by molding it using various molding methods. The molded article may further be a molded article obtained by secondarily processing a molded article, such as a sheet, obtained by the molding method described above, by thermoforming or other methods.

[0119] From the viewpoint of excellent moldability of the molded article, the MFR of this composition, measured in accordance with ASTM D1238 at 230°C and a load of 10 kgf, is preferably 0.1 to 100 g / 10 min, more preferably 1 to 100 g / 10 min. If the MFR is above the lower limit, the fluidity is good and molding in the extruder is easy, and if the MFR is below the upper limit, the occurrence of drawdown and the like when discharged from the extruder die can be suppressed and the extruder moldability is good.

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

[0121] The molded article exhibits excellent rigidity, and therefore, the Shore D hardness (after 5 seconds) of this composition, 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] While the uses of this molded product are not particularly limited, suitable examples include various known applications such as automotive parts, civil engineering and construction materials, electrical and electronic components, sanitary products, films and sheets.

[0123] <Automotive parts> Examples of the aforementioned automotive parts include automotive interior parts and automotive exterior parts. 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 beltline seals, corner moldings, glass enclosures, hood seals, glass run channels, secondary seals, various gaskets, hoses, and airbag covers. Among these, this molded product offers an excellent balance of adhesiveness and sliding properties, as well as superior low-temperature impact strength, making it particularly suitable for use in automotive parts with corner sections, such as glass run channels.

[0124] <Civil engineering / building materials supplies> Examples of the aforementioned civil engineering and construction materials include ground improvement sheets, water barriers, civil engineering materials and construction materials used for noise reduction, various gaskets and sheets for civil engineering and construction, waterproofing materials, joint materials, and building window frames.

[0125] <Electrical and Electronic Components> Examples of the aforementioned electrical and electronic components include wire insulation materials, connectors, caps, plugs, and other electrical and electronic components.

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

[0127] <Film / Sheet> Examples of the aforementioned films and sheets include intravenous fluid bags, medical containers, automotive interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort containers, pipes, transparent substrates, and sealants.

[0128] This molded product can also be used for applications other than those described above. Other uses include, for example, footwear such as shoe soles and sandals; leisure goods such as swimming fins, goggles, golf club grips, and baseball bat grips; gaskets; waterproof fabric; belts; garden hoses; anti-slip tape for stairs; and anti-slip tape for logistics pallets. [Examples]

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

[0130] <Measurement or evaluation method> Furthermore, each physical property was measured or evaluated using the following methods.

[0131] [Two-layer sheet molding method] Various two-layer sheets used in the evaluation of the sliding compositions were prepared under the following conditions, with the type of base material and sheet thickness appropriately changed. The sliding layer used pellets of the sliding composition obtained below. The base material layer was extruded using a 50 mm single-screw extruder (manufactured by Japan Steel Works Ltd.) under the temperature conditions [C1 / C2 / C3 / C4 / C5 = 160 / 170 / 180 / 190 / 200°C]. The sliding layer was extruded using a 30 mm single-screw extruder (manufactured by Plastics Engineering Laboratory Co., Ltd.) under the temperature conditions [C1 / C2 / C3 = 200 / 210 / 230°C].

[0132] [Weight average molecular weight] The weight-average molecular weight of (co)polymers and silicone compounds was measured by GPC under the following conditions. (Measurement conditions) Equipment: HLC-8120 manufactured by Tosoh Corporation Column: Polymer Laboratories PL 10u Mixed B (7.5mm ID x 30cm x 2) Detector: Differential refractive index detector (RI / built-in) Solvent: Toluene (special grade) Temperature: 40℃ Flow rate: 1.0mL / min Injection volume: 110μL Concentration: 0.1% by 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, approximately 15 mg of the sample was dissolved in 50 ml of decalin, and the specific viscosity η was measured in a 135°C oil bath. sp The specific viscosity η was measured. After diluting this decalin solution by adding 5 ml of decalin, the specific viscosity η was measured in the same manner. sp The following was measured. This dilution process was repeated twice, and when the concentration (C) was extrapolated to 0 as shown in the formula below, η sp The value of / C was determined as the intrinsic viscosity [η]. [η] = lim(η) sp / C) (C→0)

[0134] [Average particle diameter D 50 ] Average particle size D of ultra-high molecular weight polyethylene 50 This was calculated from the weight-based particle size distribution using the Coulter counter method with a Beckmann Multisizer 3.

[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 the sample was placed in a dedicated aluminum pan, and using a Diamond DSC manufactured by PerkinElmer Japan, the temperature was increased from 30°C to 230°C at 320°C / min, held at 230°C for 10 minutes, then cooled from 230°C to 30°C at 10°C / min, held at 30°C for another minute, and then the melting point was determined from the endothermic curve obtained when the temperature was increased at 10°C / min. In the event that multiple peaks were detected during DSC measurement, the peak temperature detected on the highest side was defined as the melting point (Tm).

[0136] [Ethylene content] The ethylene content of the copolymer is determined under the following conditions: 13 The result was calculated by performing 1C-NMR measurements and analyzing the obtained spectra. Equipment: Bruker BioSpin AVANCE III Cryo-500 Nuclear Magnetic Resonance Spectrometer Measurement nucleus: 13C (125MHz) Measurement mode: Single-pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Points: 64k Measurement range: 250 ppm (-55 to 195 ppm) Repeat time: 5.5 seconds Total number of times: 128 Solvent used for measurement: Orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) Sample concentration: approx. 60 mg / 0.6 mL Measurement temperature: 120℃ Window function: exponential (BF: 1.0Hz) Chemical shift criterion: δδ signal (29.73 ppm)

[0137] [Iodine value] The iodine value of the copolymer was measured according to JIS K 0070:1992, specifically the iodine value (g / 100g) of the following ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.

[0138] [Melt Flow Rate (MFR)] In accordance with ASTM D1238, the MFR of the following sliding compositions was measured at 230°C and under a 10 kgf load. Furthermore, in accordance with JIS K 7210, the MFR of the (co)polymers of the raw materials used in the following examples and comparative examples was measured at 230°C or 190°C and under a load of 2.16 kgf.

[0139] [Shore D hardness (after 5 seconds)] In accordance with ISO 7619, injection-molded square plates with a thickness of 3 mm were fabricated using the sliding composition obtained below. The Shore D hardness of a 6 mm thick laminated sheet, made by stacking two of the fabricated 3 mm thick injection-molded square plates, was measured using a Shore D hardness tester. The Shore D hardness value was determined after 5 seconds of measurement.

[0140] [Tensile properties (tensile breaking strength and tensile breaking elongation)] Using a 50t press, a 2mm thick press sheet was prepared from the sliding composition obtained below (apparatus conditions: preheating (190°C) for 8 minutes, pressurizing (190°C) for 6 minutes). A 3mm thick press sheet was then subjected to tensile tests on the prepared 3mm thick press sheet in accordance with JIS K 6251, using a JIS No. 3 dumbbell, under the conditions of a measurement temperature of 25°C and tensile speeds of 500 mm / min and 200 mm / min, to measure the tensile breaking strength (TB) and tensile breaking elongation (EB).

[0141] [Sliding characteristics (coefficient of dynamic friction and amount of wear)] A soft thermoplastic elastomer material (C700BM, manufactured by Mitsui Chemicals, Inc.) with a hardness of 70° according to JIS Duro A was used as the base material. The sliding composition obtained below was laminated onto the base material using an extrusion molding machine to a thickness of 200 μm to produce a two-layer sheet. A glass piece with a thickness of 2 mm, a tip radius R of 10 mm, and a surface roughness Ra of 3.0 μm was applied to the surface of the two-layer sheet on the sliding composition side, under a load of 1 kg and a speed of 150 mm / sec. sliding distance It was slid 20,000 times over a distance of 100 mm. The coefficient of dynamic friction after sliding and before sliding were measured in accordance with ASTM D1894-63. If the coefficient of dynamic friction after sliding is 0.25 or less, it can be said that the sliding characteristics are excellent. The amount of wear was calculated by weighing the mass (mg) of the sliding composition before and after sliding.

[0142] [Extrusion processability (adhesion of lint)] Using a soft thermoplastic elastomer material (C700BM, manufactured by Mitsui Chemicals, Inc.) with a hardness of 70° according to JIS Duro A as the base material, a two-layer sheet was continuously prepared for 30 minutes by laminating the sliding composition obtained below onto the base material using an extrusion molding machine to a thickness of 200 to 250 μm. After continuous molding for 30 minutes, the extrusion processability of the sliding composition was evaluated according to the following criteria. ○: No silicone residue was found on the die of the extrusion molding machine. ×: Silicone residue was adhering to the die of the extrusion molding machine.

[0143] [Extruderability ( molded product exterior)] For the two-layer sheets prepared for evaluation of sliding properties, the surface irregularities of the sliding composition side before sliding were observed using a surface roughness meter (model: VR-5000, manufactured by KEYENCE), a comparative measurement module (model: VR-H3J, manufactured by KEYENCE), and the VR-5000 analysis application (manufactured by KEYENCE), and the ten-point average roughness Rz of the surface irregularities was determined. molded product The exterior was evaluated according to the following criteria. ○: Rz is less than 30 μm ×: Rz is 30 μm or greater

[0144] [Extrusion processability (swell)] The pellets of the sliding composition obtained below were measured using a Toyo Seiki Seisakusho Strograph 1D model (orifice L / D=30) at a measurement temperature of 200°C, with a preheating time of 6 minutes, and a shear rate of 122 sec. -1 The swell value was measured.

[0145] [Adhesiveness] For the evaluation of sliding properties, a two-layer sheet was prepared, and test specimens were created by injection molding to bond it with a thermoplastic elastomer for injection bonding (Milastomer G800BS, manufactured by Mitsui Chemicals, Inc.). The adhesive interface of the obtained test specimens was repeatedly folded 180°, and the number of folds required until a notch appeared at the end of the specimen or the specimen fractured was evaluated according to the following criteria. ○: Folded 30 times or more ×: Folded less than 30 times

[0146] [Heat aging resistance] A two-layer sheet was prepared by laminating the sliding composition obtained below onto a substrate using an extrusion molding machine to a thickness of 200 μm, using either substrate A (C700BM, manufactured by Mitsui Chemicals, Inc.) with a hardness of JIS Duro A of 70° and an oil spreadability of 40 parts by mass, or substrate B (TS7000N, manufactured by Mitsui Chemicals, Inc.) with a hardness of JIS Duro A of 70° and an oil spreadability of 50 parts by mass, as the substrate. Each of the obtained two-layer sheets was heated at 85°C for 72 hours. The surface of the sliding composition side of each two-layer sheet 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 such as the presence of bleed material on the surface of the two-layer sheet were observed before and after heating.

[0147] <Materials used> The following oil-spreadable rubber was used as component (α), which contains ethylene-α-olefin-non-conjugated polyene copolymer (A). • Oil-applied rubber (α-1): Mitsui EPT (trademark registered) 3072EPM (manufactured by Mitsui Chemicals, Inc.) Oil-expanded rubber (α-1) is an oil-expanded ethylene-propylene-5-ethylidene-2-norbornene (ENB) copolymer rubber, with an ethylene content of 64% by mass (molar value (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. This product is produced by oil-expanding ethylene-propylene-ENB copolymer (A-1) (oil-expanded amount: 40 parts by mass). Note that the oil-expanded amount of 40 parts by mass indicates that 40 parts by mass of petroleum-based plasticizer (softener) are blended with 100 parts by mass of ethylene-propylene-ENB copolymer (A-1). • Oil-applied rubber (α-2): Mitsui EPT (trademark registered) 4100E (manufactured by Mitsui Chemicals, Inc.) Oil-expanded rubber (α-2) is an oil-expanded ethylene-propylene-ENB copolymer rubber, with an ethylene content of 57% by mass (molar value (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. The product is produced by oil-expanding ethylene-propylene-ENB copolymer (A-2) (oil-expanded amount: 50 parts by mass). • Oil-applied rubber (α-3): Mitsui EPT (trademark registered) X-3042 (manufactured by Mitsui Chemicals, Inc.) Oil-expanded rubber (α-3) is an oil-expanded ethylene-propylene-ENB copolymer rubber, with an ethylene content of 67% by mass (molar value (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. The product is produced by oil-expanding ethylene-propylene-ENB copolymer (A-3) (oil-expanded amount: 120 parts by mass).

[0148] The following copolymer was used as the propylene-based random copolymer (B1). • Copolymer (B1-1): Prime Polypropylene B241 (manufactured by Prime Polymer Co., Ltd.) Copolymer (B1-1) is a crystalline resin of propylene / ethylene random copolymer, with an MFR (compliant with JIS K 7210, 190°C, 2.16 kgf load) of 0.5 g / 10 min and a density of 910 kg / m³. 3 That is the case.

[0149] The following polymer was used as the propylene homopolymer (B2). • Homopolymer (B2-1): Prime Polypropylene E200GP (manufactured by Prime Polymer Co., Ltd.) The homopolymer (B2-1) has an MFR (compliant with JIS K 7210, 190°C, 2.16 kgf load) of 2.0 g / 10 min and a density of 900 kg / m³. 3 That is the case. • Homopolymer (B2-2): Prime Polypropylene E111G (manufactured by Prime Polymer Co., Ltd.) The homopolymer (B2-2) has an MFR (compliant with JIS K 7210, 190°C, 2.16 kgf load) of 0.5 g / 10 min and a density of 910 kg / m³. 3 That is the case.

[0150] The following copolymers were used as high-density polyethylene (C1) and high-density polyethylene (C1') for comparative examples. • Polyethylene (C1-1): Hyzex 8200B (manufactured by Prime Polymer Co., Ltd.) Polyethylene (C1-1) has an MFR (Mass Fuel Rate) of 0.03 g / 10 min (compliant with JIS K 7210, 190°C, 2.16 kgf load) and a density of 952 kg / m³. 3 That is the case. • Polyethylene (C1'-1): Hyzex 5000S (manufactured by Prime Polymer Co., Ltd.) Polyethylene (C1'-1) has an MFR (Mass Fuel Rate) of 0.82 g / 10 min (according to JIS K 7210, 190°C, 2.16 kgf load) and a density of 949 kg / m³. 3 That is the case. • Polyethylene (C1'-2): Hyzex 2200J (manufactured by Prime Polymer Co., Ltd.) Polyethylene (C1'-2) has an MFR (Mass Fuel Rate) of 5.20 g / 10 min (according to JIS K 7210, 190°C, 2.16 kgf load) and a density of 964 kg / m³. 3 That is the case.

[0151] The following copolymers were used as ultra-high molecular weight polyethylene (C2) and ultra-high molecular weight polyethylene (C2') for comparative examples. • Polyethylene (C2-1): Mipelon XM-220 (manufactured by Mitsui Chemicals, Inc.) Polyethylene (C2-1) has an intrinsic viscosity [η] of 28.0 dl / g and an average particle size D measured in decalin at 135°C. 50 The particle size is 30 μm, and the density is 938 kg / m³. 3 That is the case. • Polyethylene (C2'-1): Mipelon PM-200 (manufactured by Mitsui Chemicals, Inc.) Polyethylene (C2'-1) has an average particle size of D 50 The particle size is 10 μm, and the density is 938 kg / m³. 3 That is the case. • Polyethylene (C2'-2): Mipelon XM-330 (manufactured by Mitsui Chemicals, Inc.) Polyethylene (C2'-2) has a weight-average molecular weight of 2 million, an intrinsic viscosity [η] of 28.5 dl / g measured in decalin at 135°C, and an average particle size of D 50 The particle size is 65 μm, and the density is 938 kg / m³. 3 That is the case.

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

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

[0154] The following additives were used as other ingredients. • Softener (E-1): Diana Process PW-90 (manufactured by Idemitsu Kosan Co., Ltd., paraffin oil) • Coloring agent: F32387MM (manufactured by DIC Corporation, carbon black masterbatch, mass ratio (mass%); polyethylene (component (C3)) / carbon = 60 / 40) • Antioxidant: AO-60 (manufactured by ADEKA Corporation, phenolic antioxidant) • UV absorber: Tinuvin 326FL (manufactured by BASF Japan Ltd., benzotriazole-based UV absorber) • Weather stabilizer: Tinuvin 770 (manufactured by BASF Japan Ltd., a hindered amine (HALS) type weather stabilizer) Other additives: Alflow P10 (manufactured by NOF Corporation, fatty acid amide)

[0155] <Manufacturing of thermoplastic elastomers (EL)> [Manufacturing Example 1] Oil-applied rubber (α-1) 46.9% by mass (33.3% by mass as copolymer (A-1)), homopolymer (B2-1) 11.7% by mass, homopolymer (B2-2) 8.4% by mass, phenol resin-based crosslinking agent masterbatch (CL-1) 2.95% by mass as a crosslinking agent, antioxidant 0.07% by mass, UV absorber 0.07% by mass % A thermoplastic elastomer (EL1) was produced by thoroughly mixing 0.03% by mass of a weather stabilizer, 1.3% by mass of a carbon black masterbatch, and 28.5% by mass of a softening agent (E-1) in a Henschel mixer and extruding and kneading the mixture under the following conditions, thereby crosslinking at least a portion of the copolymer (A) with a phenolic resin-based crosslinking agent. The content (mass%) of each component (A), (B2), and (E) relative to 100.0 mass% of the obtained thermoplastic elastomer is shown in Table 1 as a composition ratio.

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

[0157] [Manufacturing Examples 2-4] 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 were changed as shown in Table 1. Thermoplastic elastomers (EL2) and (EL3) are formed by crosslinking at least a portion of copolymer (A) with a phenolic resin-based crosslinking agent, and thermoplastic elastomer (EL4) is formed by crosslinking at least a portion of copolymer (A) with an organic peroxide-based crosslinking agent.

[0158] [Table 1]

[0159] <Manufacturing of sliding compositions> [Example 1] The thermoplastic elastomer (EL1) obtained in Production Example 1 consisted of 22.2% by mass, copolymer (B1-1) 9.1% by mass, homopolymer (B2-2) 9.1% by mass, polyethylene (C1-1) 31.6% by mass, polyethylene (C2-1) 10.6% by mass, silicone compound (D-1) 8.5% by mass, silicone compound (D-3) 2.4% by mass, antioxidant 0.05% by mass, and UV absorber 0.18% by mass. % The following were thoroughly mixed in a Henschel mixer with 0.05% by mass of a weather-resistant stabilizer, 4.5% by mass of a carbon black masterbatch, and 1.82% by mass of a fatty acid amide, and extruded and kneaded under the conditions described below to obtain pellets of a sliding composition. The various physical properties of molded articles produced using the obtained pellets of composition were evaluated according to the method described above. The results are shown in Table 3. The content (mass%) of each component (A), (B1), (B2), (C1), (C2), (D), and (E) relative to 100.0% by 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-C2 120℃, C3-C4 140℃, C5-C14 200℃ Die temperature: 200℃ Screw rotation speed: 400 rpm Extrusion rate: 80 kg / h

[0161] [Examples 2-8 and Comparative Examples 1-9] In Example 1, 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 the molded articles produced using the obtained pellets of the composition were evaluated according to the method described above. The results are shown in Table 3.

[0162] [Table 2]

[0163] Table 3

Claims

1. Ethylene-α-olefin-non-conjugated polyene copolymer (A) is present in an amount of 7.0% by mass or more. A propylene-based random copolymer (B1) with a melt flow rate of 0.1 to 4.0 g / 10 min, measured at 190°C and a load of 2.16 kgf, is present in an amount of 6.0% by mass or more. A propylene homopolymer (B2) with a melt flow rate of 0.1 to 4.0 g / 10 min, measured at 190°C and a load of 2.16 kgf, is present in an amount of 10.0% by mass or more. Density of 940-970 kg / m³ 3 The mixture contains 15.0% by mass or more of high-density polyethylene (C1), which has a melt flow rate of 0.1 g / 10 min or less as measured at 190°C and a load of 2.16 kgf. The intrinsic viscosity [η] measured in decalin solvent at 135°C was 10–40 dl / g, and the weight-average particle size D 50 The particle size is 22-50 μm, and the density is 940 kg / m³. 3 Ultra-high molecular weight polyethylene (C2) less than 10.0% by mass or more, and It contains 5.0 to 8.0% by mass of a silicone compound (D) having a kinematic viscosity of 3,000 to 1,000,000 cSt at 25°C. The total content of the aforementioned components (A), (B1), (B2), (C1), (C2), and (D) is 100.0% by mass or less. A sliding composition comprising at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) crosslinked with a phenol resin-based crosslinking agent.

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

3. The sliding composition according to claim 1 or 2, wherein the Shore D hardness measured 5 seconds after measurement in accordance with ISO 7619 is 30 to 60.

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-based random copolymer (B1) and the propylene homopolymer (B2) is 20.0% by mass or more.

6. The content of the propylene-based random copolymer (B1) is 9.0 to 15.0% by mass, and the density of the propylene-based random copolymer (B1) is 900 to 920 kg / m³. 3 The sliding composition according to claim 1 or 2.

7. The content of the propylene homopolymer (B2) is 10.0 to 18.0% by mass, and the density of the propylene homopolymer (B2) is 900 to 920 kg / m³. 3 The sliding composition according to claim 1 or 2.

8. The sliding composition according to claim 1 or 2, wherein the mass ratio of the propylene homopolymer (B2) to the propylene random copolymer (B1), (B2) / (B1), is 1.0 to 3.

0.

9. The content of the aforementioned ultra-high molecular weight polyethylene (C2) is 10.0 to 30.0% by mass, and the weight-average particle size D 50 The sliding composition according to claim 1 or 2, wherein the thickness 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. Ethylene-α-olefin-non-conjugated polyene copolymer (A) is present in an amount of 7.0% by mass or more. A propylene-based random copolymer (B1) with a melt flow rate of 0.1 to 4.0 g / 10 min, measured at 190°C and a load of 2.16 kgf, is present in an amount of 6.0% by mass or more. A propylene homopolymer (B2) with a melt flow rate of 0.1 to 4.0 g / 10 min, measured at 190°C and a load of 2.16 kgf, is present in an amount of 10.0% by mass or more. Density of 940-970 kg / m³ 3 The mixture contains 15.0% by mass or more of high-density polyethylene (C1), which has a melt flow rate of 0.1 g / 10 min or less as measured at 190°C and a load of 2.16 kgf. The intrinsic viscosity [η] measured in a decalin solvent at 135°C is 10 to 40 dl / g, and the weight average particle diameter D 50 is 22 to 50 μm, and the density is less than 940 kg / m 3 Ultra-high molecular weight polyethylene (C2) of less than 10.0 mass% or more, and It contains 5.0 to 8.0% by mass of a silicone compound (D) having a kinematic viscosity of 3,000 to 1,000,000 cSt at 25°C. The total content of the aforementioned components (A), (B1), (B2), (C1), (C2), and (D) is 100.0% by mass or less. A method for producing a sliding composition comprising at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) being crosslinked, A method for producing a sliding composition, comprising the step of crosslinking at least a portion of the ethylene-α-olefin-nonconjugated polyene copolymer (A) with a phenol resin-based crosslinking agent.

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