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WO2023002932A1 - Composition d'élastomère thermoplastique et corps moulé comprenant ladite composition - Google Patents

Composition d'élastomère thermoplastique et corps moulé comprenant ladite composition Download PDF

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Publication number
WO2023002932A1
WO2023002932A1 PCT/JP2022/027823 JP2022027823W WO2023002932A1 WO 2023002932 A1 WO2023002932 A1 WO 2023002932A1 JP 2022027823 W JP2022027823 W JP 2022027823W WO 2023002932 A1 WO2023002932 A1 WO 2023002932A1
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Prior art keywords
thermoplastic elastomer
structural units
mass
polymer block
units derived
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Japanese (ja)
Inventor
康裕 黒田
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Kuraray Plastics Co Ltd
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Kuraray Plastics Co Ltd
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Priority to JP2023536728A priority Critical patent/JPWO2023002932A1/ja
Priority to CN202280050756.XA priority patent/CN117677668A/zh
Publication of WO2023002932A1 publication Critical patent/WO2023002932A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a thermoplastic elastomer composition and a molded article made of the thermoplastic elastomer composition.
  • vulcanized rubber such as silicone rubber, butyl rubber, or ethylene propylene diene rubber (EPDM) has been widely used as a material for damping materials used in various industrial equipment, consumer equipment, automobiles, etc.
  • EPDM ethylene propylene diene rubber
  • styrenic thermoplastic elastomers have been proposed for the purpose of environmental friendliness and cost reduction, but styrenic thermoplastic elastomers have the problem of insufficient heat resistance.
  • Patent Document 1 discloses a hydrogenated thermoplastic styrene elastomer [I] or an elastomer mixture of a hydrogenated thermoplastic styrene elastomer [I] and a hydrogenated thermoplastic styrene elastomer [II], a filler, a
  • a heat-resistant, vibration-damping elastomeric composition comprising a softener, polyphenylene ether, and polypropylene is disclosed, and said composition is said to have excellent heat resistance and vibration-damping properties.
  • Patent Document 2 discloses a thermoplastic elastomer composition comprising a hydrogenated block copolymer, a polypropylene resin, a polyphenylene ether resin, and a non-aromatic softening agent, and the resin composition is Excellent compression set and elongation set are described.
  • JP 2010-24275 A International Publication No. 2018/139122
  • thermoplastic elastomer composition disclosed in Patent Document 1 is inferior in restoring force and insufficient in heat resistance. It was also found that the thermoplastic elastomer composition disclosed in Patent Document 2 is inferior in damping properties and insufficient in heat resistance.
  • An object of the present invention is to provide a thermoplastic elastomer composition excellent in damping properties, restoring properties and heat resistance in view of the problems of the prior art described above. Another object of the present invention is to provide a thermoplastic elastomer composition having an appropriate hardness.
  • thermoplastic elastomer comprises a thermoplastic elastomer (a1) and a thermoplastic elastomer (a2) at a mass ratio of 90:10 to 45:55
  • thermoplastic elastomer (a1) is a block composed of a polymer block (X1) composed of structural units derived from an aromatic vinyl compound and a polymer block (Y1) composed of structural units derived from a conjugated diene compound.
  • thermoplastic elastomer (a2) is a block composed of a polymer block (X2) composed of structural units derived from an aromatic vinyl compound and a polymer block (Y2) composed of structural units derived from a conjugated diene compound.
  • thermoplastic elastomer (a2) It is a copolymer and has a weight average molecular weight of 50,000 or more and 150,000 or less, and the content of structural units derived from the aromatic vinyl compound in the thermoplastic elastomer (a2) is The total content of 1,2-bond units and 3,4-bond units of structural units derived from the conjugated diene compound in the thermoplastic elastomer (a2) is , 50 mol% or more based on all structural units derived from the conjugated diene compound, In a transmission electron microscope image of the thermoplastic elastomer composition, the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase containing the thermoplastic elastomer (a) is 2 ⁇ m or less, Three test pieces having a thickness of 2 mm obtained by injection molding the thermoplastic elastomer composition at 230° C.
  • thermoplastic elastomer (a2) has a hydrogenation rate of 20% or less.
  • thermoplastic elastomer (a2) has an order-disorder transition temperature of 280° C. or lower.
  • thermoplastic elastomer composition that is excellent in damping properties, resilience and heat resistance and has appropriate hardness.
  • FIG. 4 is a transmission electron microscope image used to determine the maximum length of the polyphenylene ether resin (b) of the thermoplastic elastomer composition prepared in Example 2.
  • FIG. 4 is a transmission electron microscope image used to determine the maximum length of the polyphenylene ether resin (b) of the thermoplastic elastomer composition prepared in Comparative Example 3.
  • FIG. 4 is a transmission electron microscope image used to determine the maximum length of the polyphenylene ether resin (b) of the thermoplastic elastomer composition prepared in Comparative Example 3.
  • thermoplastic elastomer composition of the present invention is (a) a thermoplastic elastomer; (b) a polyphenylene ether resin; and (c) a rubber softener.
  • the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase containing the thermoplastic elastomer (a) is 2 ⁇ m or less.
  • the present inventors have unexpectedly found that the thermoplastic elastomer composition containing the above components (a) to (c) allows the polyphenylene ether resin (b) in the thermoplastic elastomer composition to be the thermoplastic elastomer in the prior art. It has been found that the thermoplastic elastomer composition can be dispersed to a higher degree than the composition, and as a result, the thermoplastic elastomer composition can satisfactorily exhibit all of damping properties, resilience and heat resistance.
  • thermoplastic elastomer composition could exhibit excellent heat resistance even though it contained a low-molecular-weight thermoplastic elastomer (thermoplastic elastomer (a2)) known to have low heat resistance.
  • thermoplastic elastomer (a2) a low-molecular-weight thermoplastic elastomer known to have low heat resistance.
  • thermoplastic elastomer (a2) a thermoplastic elastomer having a specific molecular structure and weight average molecular weight is a thermoplastic elastomer composition.
  • thermoplastic elastomer (a2) can selectively disperse (compatibility) the polyphenylene ether resin (b) in the polymer block (X2) of the thermoplastic elastomer (a2), as a result, the polyphenylene ether resin (b) and the polymer block (X2 ), and compatibility between the polyphenylene ether resin (b) and the polymer block (X2) and the polymer block (X1), that is, the polyphenylene ether resin (b) and the thermoplastic elastomer (a1) and the thermoplastic It is believed that the compatibility with the plastic elastomer (a2) can be improved, and as a result, the obtained thermoplastic elastomer composition is endowed with high heat resistance in addition to excellent damping properties and resilience. be done.
  • the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less. Since the smaller the maximum length of the polyphenylene ether resin (b), the more highly dispersed the polyphenylene ether resin (b) is, the lower limit of the maximum length of the polyphenylene ether resin (b) is not limited.
  • the lower limit of the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase corresponds to the detection limit in a transmission electron microscope image of the thermoplastic elastomer composition at a magnification of 10,000 times, and is usually 0.0001 ⁇ m.
  • the polyphenylene ether resin (b) is highly dispersed in the matrix phase, making it difficult to clearly distinguish it as the polyphenylene ether resin (b) in a transmission electron microscope image.
  • the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase is 2 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less in a transmission electron microscope image.
  • the maximum length of the polyphenylene ether resin (b) dispersed in the matrix phase in the transmission electron microscope image of the thermoplastic elastomer composition can be measured by the method described in Examples below.
  • the matrix phase comprises a rubber softener (c) in addition to the thermoplastic elastomer (a).
  • the desired maximum major diameter of the polyphenylene ether resin (b) dispersed in the matrix phase is obtained by the thermoplastic elastomer composition containing the specific component (a) and the components (b) and (c). It can be adjusted below the upper limit.
  • the thermoplastic elastomer (a) comprises a thermoplastic elastomer (a1) and a thermoplastic elastomer (a2) at a mass ratio of 90:10 to 45:55. If the thermoplastic elastomer (a1) is too much and the mass ratio deviates from the range of 90:10 to 45:55, it is difficult to obtain the desired damping properties and heat resistance. Moreover, if the thermoplastic elastomer (a1) is too small and the mass ratio deviates from the range of 90:10 to 45:55, it is difficult to obtain the desired heat resistance.
  • the mass ratio is preferably 90:10 to 50:50, more preferably 90:10 to 55:45, and still more preferably 90:10 to 60:40. , or preferably 85:15 to 45:55, more preferably 85:15 to 50:50, still more preferably 85:15 to 55:45, particularly preferably 85:15 to 60:40, or preferably 80:20 to 45:55, more preferably 80:20 to 50:50, still more preferably 80:20 to 55:45, particularly preferably 80:20 to 60:40, or preferably 75:25 to 45 :55, more preferably 75:25 to 50:50, still more preferably 75:25 to 55:45, particularly preferably 75:25 to 60:40.
  • thermoplastic elastomer (a1) is a block composed of a polymer block (X1) composed of structural units derived from an aromatic vinyl compound and a polymer block (Y1) composed of structural units derived from a conjugated diene compound. It is a copolymer.
  • the thermoplastic elastomer (a1) is also referred to as "block copolymer (a1)".
  • a polymer block composed of structural units means that the structural units are the largest in the polymer block, and the content of the structural units in the polymer block is Based on the mass of the polymer block, it is preferably 70% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.
  • a polymer block (X1) composed of structural units derived from an aromatic vinyl compound means that the polymer block (X1) has the largest number of "structural units derived from an aromatic vinyl compound.”
  • the content of the structural unit derived from the aromatic vinyl compound in the polymer block (X1) is preferably 70% by mass or more, more preferably 90% by mass or more, based on the mass of the polymer block (X1).
  • thermoplastic elastomer (a2) particularly preferably 95% by mass or more, and may be 100% by mass.
  • the same meaning applies to the thermoplastic elastomer (a2), etc., which will be described later.
  • the content of various structural units in the thermoplastic elastomer can be determined by 1 H-NMR spectrum or the like.
  • the weight average molecular weight of the block copolymer (a1) is greater than 150,000, preferably 200,000 or more, and 500,000 or less, preferably 400,000 or less.
  • the thermoplastic elastomer composition has desired mechanical properties, flexibility and In addition to damping properties, melt viscosity for more preferably dispersing the polyphenylene ether resin (b) tends to be imparted.
  • the weight average molecular weight of the block copolymer can be calculated by performing gel permeation chromatography measurement and converting to polystyrene.
  • the polymer block (X1) preferably has a weight average molecular weight of 30,000 to 250,000, more preferably 40,000 to 150,000.
  • the polymer block (Y1) preferably has a weight average molecular weight of 120,000 to 400,000, more preferably 150,000 to 350,000.
  • the block copolymer (a1) preferably has one or more polymer blocks (X1) and one or more polymer blocks (Y1) from the viewpoint of flexibility and non-adhesiveness. From the viewpoint of flexibility, heat resistance and mechanical properties, the block copolymer (a1) preferably has two or more polymer blocks (X1) and one or more polymer blocks (Y1).
  • the bonding mode between polymer block (X1) and polymer block (Y1) may be linear, branched, radial, or any combination thereof, but linear bonding is preferred.
  • the block copolymer (a1) has a diblock structure represented by X1-Y1, represented by X1-Y1-X1, where the polymer block (X1) is represented by X1 and the polymer block (Y1) is represented by Y1. It can have a triblock structure, a multiblock structure represented by (X1-Y1) n and (X1-Y1) n -X1 (where n is an integer of 2 or more), and the like. Among these, the triblock structure represented by X1-Y1-X1 is preferable from the viewpoint of heat resistance, mechanical properties, handleability and the like.
  • each polymer block (X1) and each polymer block (Y1) may be blocks with the same configuration or blocks with different configurations.
  • two polymer blocks (X1) in the triblock structure represented by X1-Y1-X1 may have the same or different types of aromatic vinyl compounds constituting them.
  • aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, 2,4-dimethylstyrene, 2, 4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene and the like.
  • the aromatic vinyl compounds are preferably styrene and styrene derivatives.
  • the aromatic vinyl compound may be used alone or in combination of two or more.
  • the polymer block (X1) may have structural units derived from other copolymerizable monomers in addition to structural units derived from the aromatic vinyl compound.
  • structural units derived from other copolymerizable monomers is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the mass of the polymer block (X1).
  • copolymerizable monomers examples include ionic polymerizable monomers such as 1-butene, pentene, hexene, 1,3-butadiene (also simply referred to as “butadiene”), isoprene, and methyl vinyl ether. . These other copolymerizable monomers may be used alone or in combination of two or more.
  • the binding form thereof may be random, tapered, or the like. may be in the form of
  • the content of the structural unit derived from the aromatic vinyl compound in the block copolymer (a1) is 10% by mass or more, preferably 15% by mass or more, based on the total structural units constituting the block copolymer (a1). , more preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the thermoplastic elastomer composition tends to exhibit superior flexibility.
  • conjugated diene compounds examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene.
  • the conjugated diene compounds may be used alone or in combination of two or more. From the viewpoint of damping properties, the conjugated diene compound is preferably butadiene, isoprene, or a mixture thereof.
  • the polymer block (Y1) When the polymer block (Y1) is composed of structural units derived from a mixture of isoprene and butadiene, the polymer block (Y1) contains a 2-methyl-2-butene-1,4-diyl group derived from isoprene. , isopropenylethylene and/or 1-methyl-1-vinylethylene groups, and 2-butene-1,4-diyl and/or vinylethylene groups derived from butadiene.
  • the total content of 1,2-bond units and 3,4-bond units of structural units derived from the conjugated diene compound in the thermoplastic elastomer (a1) (hereinafter also referred to as “vinyl bond content”) is the conjugated diene It is preferably 10 mol % or more, more preferably 20 mol % or more, and preferably 50 mol % or less based on all structural units derived from the compound.
  • vinyl bond content in the thermoplastic elastomer (a1) is at least the lower limit value and not more than the upper limit value, an increase in adhesiveness is suppressed, and a composition with excellent handleability can be easily obtained.
  • the polymer block (Y1) may have structural units derived from other copolymerizable monomers in addition to structural units derived from the conjugated diene compound.
  • the polymer block (Y1) has structural units derived from other copolymerizable monomers in addition to structural units derived from the conjugated diene compound, structural units derived from other copolymerizable monomers
  • the content is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the mass of the polymer block (Y1).
  • Examples of other copolymerizable monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Anionically polymerizable monomers such as aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene and the like can be mentioned.
  • the binding form thereof may be random, tapered, or the like. may be in the form
  • thermoplastic elastomer (a1) may optionally have functional groups such as carboxyl groups, hydroxyl groups, acid anhydride groups, amino groups and epoxy groups in the molecular chain and/or at the molecular ends as long as the effects of the present invention are not impaired. You may have 1 type, or 2 or more types.
  • the block copolymer (a1) is preferably hydrogenated.
  • the hydrogenation rate of the polymer block (Y1) of the block copolymer (a1) is preferably 90% or higher, more preferably 95% or higher, particularly preferably 99% or higher.
  • the hydrogenation rate is usually 100% or less.
  • the hydrogenation rate of the block copolymer (a1) can be measured by iodine value measurement, infrared spectrophotometer (IR), nuclear magnetic resonance method ( 1 H-NMR, 13 C-NMR), and the like.
  • thermoplastic elastomer (a1) ⁇ Method for preparing thermoplastic elastomer (a1)>
  • examples of the method for polymerizing the thermoplastic elastomer (a1) include ionic polymerization methods such as anionic polymerization method and cationic polymerization method, single-site polymerization method, and radical polymerization method.
  • thermoplastic elastomer (a1) using an anionic polymerization method An example of a method for preparing the thermoplastic elastomer (a1) using an anionic polymerization method is shown below.
  • an alkyllithium compound or the like as a polymerization initiator, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane, and the desired molecular structure or molecular weight is reached.
  • the block copolymer is prepared by adding an active hydrogen compound such as alcohols, carboxylic acids or water to terminate the polymerization.
  • alkyllithium compounds include alkyllithium compounds in which the alkyl group has 1 to 10 carbon atoms.
  • the alkyllithium compounds may be used singly or in combination of two or more. Methyllithium, ethyllithium, butyllithium and pentyllithium are particularly preferred.
  • the amount of the polymerization initiator such as the alkyllithium compound to be used is determined according to the desired peak top molecular weight of the thermoplastic elastomer (a1).
  • the amount of the polymerization initiator is usually 0.01 to 0.2 parts by weight per 100 parts by weight of all the monomers used for polymerization.
  • the polymerization reaction is usually carried out at a reaction temperature of 0 to 80°C for 0.5 to 50 hours.
  • Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N,N,N',N'-tetramethylethylenediamine, N-methylmorpholine. and other amine compounds.
  • the amount of these Lewis bases to be used is preferably about 0.1 to 1000 times the number of moles of lithium in the alkyllithium compound used as the polymerization initiator.
  • an inert organic solvent such as n-hexane or cyclohexane that is inert to the hydrogenation reaction and the hydrogenation catalyst is used in the presence of a hydrogenation catalyst.
  • a method of dissolving the unhydrogenated block copolymer in and then reacting with molecular hydrogen is preferably used.
  • a hydrogenation reaction may be subsequently carried out in the presence of a hydrogenation catalyst in an inert organic solvent without isolating the prepared block copolymer, and this hydrogenation method is preferred.
  • hydrogenation catalysts examples include Raney nickel; heterogeneous catalysts such as metal-supported catalysts in which metals such as Pt, Pd, Ru, Rh and Ni are supported on simple substances such as carbon, alumina and diatomaceous earth; transition metal compounds and alkylaluminum compounds or Ziegler-type catalysts in combination with alkyllithium compounds or the like.
  • the hydrogenation reaction is usually carried out at a hydrogen pressure of 0.1 to 20 MPa and a reaction temperature of 20° C. to 250° C. for 0.1 to 100 hours. After preparation of the hydrogenated block copolymer, the hydrogenation catalyst is removed by filtration.
  • reaction solution The reaction solution of the unhydrogenated block copolymer or the filtrate of the hydrogenated block copolymer after filtration (reaction solution) is usually heated to 40 to 150° C., preferably 60 to 150° C., and if necessary, a fatty acid salt or A surfactant such as a polyoxyalkylene derivative is added and mixed. While supplying steam of 1 MPa at a rate of 40 to 60 parts by mass/hour with respect to 100 parts by mass of the mixture, the mixture is supplied to hot water of 80 to 130°C at a rate of 100 parts by mass/hour. By doing so, steam stripping is carried out.
  • an inert organic solvent such as a saturated hydrocarbon boils or azeotropes the inert organic solvent with water
  • the steam stripping is carried out at a temperature above the boiling temperature or above the azeotropic temperature and up to 150°C. do.
  • it is dehydrated to a water content of 55% by mass/WB (wet base, hereinafter the same) or less, preferably 45% by mass/WB or less, using a compression water squeezer, and a screw extruder type dryer, expander dryer, conductive heat transfer type
  • a powdery thermoplastic elastomer (a1) having a moisture content of 0.1 mass %/WB or less can be prepared.
  • thermoplastic elastomer (a2) is a block composed of a polymer block (X2) composed of structural units derived from an aromatic vinyl compound and a polymer block (Y2) composed of structural units derived from a conjugated diene compound. It is a copolymer.
  • the thermoplastic elastomer (a2) is also referred to as "block copolymer (a2)".
  • the weight average molecular weight of the block copolymer (a2) is 50,000 or more, preferably 70,000 or more, and 150,000 or less, preferably 130,000 or less.
  • the thermoplastic elastomer composition tends to exhibit excellent resilience and heat resistance.
  • the polymer block (X2) preferably has a weight average molecular weight of 5,000 to 20,000, more preferably 10,000 to 15,000.
  • the polymer block (Y2) preferably has a weight average molecular weight of 20,000 to 140,000, more preferably 50,000 to 110,000.
  • the block copolymer (a2) preferably has one or more polymer blocks (X2) and one or more polymer blocks (Y2).
  • the block copolymer (a2) preferably has two or more polymer blocks (X2) and one or more polymer blocks (Y2) from the viewpoint of damping properties, flexibility, heat resistance and mechanical properties.
  • the bonding mode between the polymer block (X2) and the polymer block (Y2) may be linear, branched, radial, or any combination thereof, but a linear bonding mode is preferred.
  • the block copolymer (a2) has a diblock structure represented by X2-Y2, represented by X2-Y2-X2, where X2 represents the polymer block (X2) and Y2 represents the polymer block (Y2).
  • X2-Y2 a multiblock structure represented by (X2-Y2) n and (X2-Y2) n -X2 (where n represents an integer of 2 or more), and the like.
  • the triblock structure represented by X2-Y2-X2 is preferable from the viewpoint of not only vibration damping properties but also heat resistance, mechanical properties and handleability.
  • each polymer block (X2) and each polymer block (Y2) may be blocks with the same configuration or blocks with different configurations.
  • the two polymer blocks (X2) in the triblock structure represented by X2-Y2-X2 may have the same or different types of aromatic vinyl compounds constituting them.
  • aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, 2,4-dimethylstyrene, 2, 4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene and the like.
  • the aromatic vinyl compounds are preferably styrene and styrene derivatives.
  • the aromatic vinyl compound may be used alone or in combination of two or more.
  • the polymer block (X2) may have structural units derived from other copolymerizable monomers in addition to structural units derived from the aromatic vinyl compound.
  • structural units derived from other copolymerizable monomers is preferably 10% by mass or less, more preferably 5% by mass or less, based on the mass of the polymer block (X2).
  • copolymerizable monomers examples include ionically polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene and methyl vinyl ether. These other copolymerizable monomers may be used alone or in combination of two or more.
  • the binding form thereof may be random, tapered, or the like. may be in the form of
  • the content of the structural unit derived from the aromatic vinyl compound in the block copolymer (a2) is 2% by mass or more, preferably 5% by mass or more, based on the total structural units constituting the block copolymer (a2). , more preferably 10% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the thermoplastic elastomer composition has superior flexibility and vibration damping properties, as well as higher heat resistance. easy to express.
  • conjugated diene compounds examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene.
  • the conjugated diene compounds may be used alone or in combination of two or more. From the viewpoint of damping properties, the conjugated diene compound is preferably butadiene, isoprene, or a mixture thereof.
  • the polymer block (Y2) is composed of structural units derived from a mixture of isoprene and butadiene
  • the polymer block (Y2) contains a 2-methyl-2-butene-1,4-diyl group derived from isoprene. , isopropenylethylene and/or 1-methyl-1-vinylethylene groups, and 2-butene-1,4-diyl and/or vinylethylene groups derived from butadiene.
  • the total content of 1,2-bond units and 3,4-bond units (vinyl bond content) in the structural units derived from the conjugated diene compound in the thermoplastic elastomer (a2) is the total structural units derived from the conjugated diene compound. is 50 mol % or more, preferably 55 mol % or more, preferably 80 mol % or less, more preferably 70 mol % or less, still more preferably less than 63 mol %.
  • the vinyl bond content in the thermoplastic elastomer (a2) is not less than the lower limit and not more than the upper limit, the thermoplastic elastomer composition exhibits superior vibration damping properties and resilience, as well as higher heat resistance. easy to express.
  • the polymer block (Y2) may have structural units derived from other copolymerizable monomers in addition to structural units derived from the conjugated diene compound.
  • the polymer block (Y2) has structural units derived from other copolymerizable monomers in addition to structural units derived from the conjugated diene compound, structural units derived from other copolymerizable monomers
  • the content is preferably 30% by mass or less, more preferably 10% by mass or less, based on the mass of the polymer block (Y2).
  • Examples of other copolymerizable monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Anionically polymerizable monomers such as aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene and the like can be mentioned.
  • the binding form thereof may be random, tapered, or the like. may be in the form
  • thermoplastic elastomer (a2) may optionally have functional groups such as carboxyl groups, hydroxyl groups, acid anhydride groups, amino groups and epoxy groups in the molecular chain and/or at the molecular ends as long as the effects of the present invention are not impaired. You may have 1 type, or 2 or more types.
  • the unsaturated double bonds based on the conjugated diene compound of the thermoplastic elastomer (a2) may be hydrogenated within the range not impairing the object of the present invention.
  • the hydrogenation rate of the polymer block (Y2) composed of structural units derived from the conjugated diene compound of the thermoplastic elastomer (a2) is preferably 20% or less, more preferably 17% or less, and more preferably 14% or less. , More preferably 12% or less, more preferably 10% or less, still more preferably 8% or less, still more preferably 6% or less, still more preferably 4% or less, still more preferably 2% or less, particularly preferably 0% (non hydrogenation).
  • polymer block (Y2) of block copolymer (a2) is non-hydrogenated.
  • the polymer block (Y2) has a hydrogenation rate of the upper limit or less or is non-hydrogenated, the polyphenylene ether resin (b) and the polymer block (X2) and the polymer block (X1) phase Solubility, especially compatibility with the polymer block (X2) tends to be improved.
  • the thermoplastic elastomer composition of the present invention is likely to be imparted with a higher degree of heat resistance in addition to superior damping properties and resilience.
  • the hydrogenation rate of the polymer block (Y2) of the block copolymer (a2) can be determined by iodine value measurement, infrared spectrophotometer (IR), nuclear magnetic resonance ( 1 H-NMR, 13 C-NMR), and the like. can be measured.
  • the thermoplastic elastomer (a2) has an order-disorder transition temperature (ODTT) of 280°C or lower, preferably 270°C or lower, more preferably 260°C or lower.
  • ODTT order-disorder transition temperature
  • the thermoplastic elastomer (a2) has an order-disorder transition temperature equal to or lower than the above upper limit, the dispersibility of the polyphenylene ether resin (b) in the matrix phase is more easily improved, and the thermoplastic elastomer composition of the present invention is more A higher degree of heat resistance is likely to be imparted in addition to excellent damping properties and resilience.
  • the lower limit of the thermoplastic elastomer (a2) is not particularly limited, it is usually 200°C or higher.
  • the order-disorder transition temperature can be measured by the method described in Examples below.
  • the order-disorder transition temperature of the thermoplastic elastomer (a2) is adjusted to the upper limit value or less by the weight average molecular weight of the thermoplastic elastomer (a2), the vinyl bond content and/or the hydrogenation rate of the polymer block (X2). can.
  • thermoplastic elastomer (a2) examples include ionic polymerization methods such as anionic polymerization method and cationic polymerization method, single-site polymerization method, and radical polymerization method.
  • ionic polymerization methods such as anionic polymerization method and cationic polymerization method, single-site polymerization method, and radical polymerization method.
  • An example of a method for preparing the thermoplastic elastomer (a2) using an anionic polymerization method is shown below. First, using an alkyllithium compound or the like as a polymerization initiator, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane, and the desired molecular structure or molecular weight is reached. , the block copolymer is prepared by adding an active hydrogen compound such as alcohols, carboxylic acids or water to terminate the polymerization.
  • an active hydrogen compound such as alcohols, carboxy
  • alkyllithium compounds include alkyllithium compounds in which the alkyl group has 1 to 10 carbon atoms.
  • the alkyllithium compounds may be used singly or in combination of two or more. Methyllithium, ethyllithium, butyllithium and pentyllithium are particularly preferred.
  • the amount of the polymerization initiator such as the alkyllithium compound to be used is determined by the desired peak top molecular weight of the thermoplastic elastomer (a2).
  • the amount of the polymerization initiator is usually 0.01 to 0.2 parts by weight per 100 parts by weight of all the monomers used for polymerization.
  • the polymerization reaction is usually carried out at a reaction temperature of 0 to 80°C for 0.5 to 50 hours.
  • Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N,N,N',N'-tetramethylethylenediamine, N-methylmorpholine. and other amine compounds.
  • the amount of these Lewis bases to be used is preferably about 0.1 to 1000 times the number of moles of lithium in the alkyllithium compound used as the polymerization initiator.
  • the prepared unhydrogenated block copolymer When the prepared unhydrogenated block copolymer is subjected to a hydrogenation reaction, it may be carried out in the same manner as the hydrogenation reaction in the method for preparing the thermoplastic elastomer (a1). After preparation of the hydrogenated block copolymer, the hydrogenation catalyst is removed by filtration.
  • reaction solution The reaction solution of the unhydrogenated block copolymer or the filtrate of the hydrogenated block copolymer after filtration (reaction solution) is subjected to heating, steam stripping, dehydration and drying in the same manner as in the method for preparing the thermoplastic elastomer (a1). By doing so, a powdery thermoplastic elastomer (a2) having a water content of 0.1% by mass/WB or less can be prepared.
  • the thermoplastic elastomer composition of the present invention can exhibit excellent compression set at high temperatures.
  • the polyphenylene ether resin (b) for example, the following general formula (1): [wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group or a nitro group]
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group or a nitro group
  • a polymer having a structural unit represented by can be used.
  • R 1 and R 2 are preferably alkyl groups, more preferably alkyl groups having 1 to 4 carbon atoms, and R 3 and R 4 are preferably hydrogen atoms or C 1 ⁇ 4 alkyl groups.
  • polyphenylene ether resins (b) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl -1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6-dichloromethyl-1,4-phenylene) ether, poly(2,6-dibromomethyl) -1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-ditolyl-1,4-phenylene) ether, poly(2,6-dichloro-1) ,4-phenylene) ether, poly(2,6-dibenzyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl
  • the polyphenylene ether resin (b) may be modified with a modifying agent having a polar group.
  • polar groups include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters, acid azides, sulfone groups, nitrile groups, cyano groups, isocyanate esters, amino groups, imide groups, hydroxyl groups, epoxy groups. , an oxazoline group and a thiol group.
  • the number average molecular weight of the polyphenylene ether resin (b) is preferably 1,000 to 100,000, and more preferably 6,000 to 60, especially considering the balance of various physical properties (heat resistance and compression set). 000.
  • the amount of the polyphenylene ether resin (b) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 100 parts by mass or less, more preferably 100 parts by mass of the thermoplastic elastomer (a). It is 60 parts by mass or less.
  • the amount of the polyphenylene ether resin (b) is at least the lower limit, the thermoplastic elastomer composition tends to exhibit excellent high-temperature compression set.
  • the amount of the polyphenylene ether resin (b) is equal to or less than the upper limit, the thermoplastic elastomer composition tends to exhibit excellent high-temperature compression set while ensuring suitable flexibility of the thermoplastic elastomer composition. .
  • polyphenylene ether (b) The production method of polyphenylene ether (b) is not particularly limited, and can be produced, for example, by a conventionally known method.
  • Commercially available examples of polyphenylene ether (b) include PPO 640 (trade name) manufactured by SABIC Innovative Plastics Japan LLC and PX100F manufactured by Mitsubishi Engineering Plastics.
  • the rubber softener (c) imparts flexibility to the thermoplastic elastomer composition of the present invention.
  • rubber softeners (c) include paraffinic, naphthenic or aromatic process oils; phthalic acid derivatives such as dioctyl phthalate or dibutyl phthalate; white oils; mineral oils; Liquid polydienes such as co-oligomer; liquid paraffin; polybutene; low molecular weight polyisobutylene; Hydrogenated products and the like can be mentioned. Rubber softeners (c) may be used alone or in combination of two or more. From the viewpoint of compatibility with the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2), paraffinic process oil, liquid co-oligomer of ethylene and ⁇ -olefin, or liquid paraffin are preferred.
  • the weight average molecular weight of the rubber softener (c) is preferably 700 or more, more preferably 750 or more, and preferably 1500 or less, more preferably 1400 or less. If the weight average molecular weight of the rubber softener (c) is at least the lower limit, the flexibility and mechanical strength will be better, and if it is at most the upper limit, the moldability will be better.
  • the kinematic viscosity (40° C.) of the softener for rubber (c) is preferably 80 mm 2 /s or higher, more preferably 90 mm 2 /s or higher, still more preferably 100 mm 2 /s or higher, and particularly preferably 150 mm 2 /s or higher. , more preferably 200 mm 2 /s or more, preferably 500 mm 2 /s or less, more preferably 400 mm 2 /s or less, still more preferably 390 mm 2 /s or less.
  • kinematic viscosity (40°C) of the softening agent (c) is at least the lower limit, the flexibility and non-tackiness will be better, and if it is at most the upper limit, the moldability will be better.
  • Kinematic viscosity can be measured according to JIS K 2283, for example.
  • the production method of the rubber softener (c) is not particularly limited, and can be produced, for example, by a conventionally known method.
  • Examples of commercially available rubber softeners (c) include Diana Process Oil PW series (paraffin oil) manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil NR series (naphthenic oil) manufactured by Idemitsu Kosan Co., Ltd., and NIKKO. OIL PRODUCTS Co., Ltd. NOBEL process oil AB series (aromatic oil) and the like.
  • the amount of the softener for rubber (c) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more, based on 100 parts by mass of the thermoplastic elastomer (a). is 300 parts by mass or less, more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less.
  • the amount of the rubber softener (c) is at least the lower limit, the thermoplastic elastomer composition tends to have better flexibility.
  • the amount of the rubber softening agent (c) is equal to or less than the upper limit, the thermoplastic elastomer composition tends to have better mechanical strength.
  • the thermoplastic elastomer composition of the present invention may further contain polypropylene for the purpose of imparting flexibility.
  • polypropylene (d) include homopolypropylene, random polypropylene copolymers and block polypropylene copolymers. From the viewpoint of heat resistance, homopolypropylene is preferred.
  • Polypropylene preferably has a melt flow rate (MFR) of 1 to 100 g/10 minutes, more preferably 5 to 85 g/10 minutes, and even more preferably 10 to 60 g/10 minutes at 230°C in accordance with JIS K 7210.
  • thermoplastic elastomer composition of the present invention contains polypropylene (d), the content of polypropylene (d) does not impair the effects of the present invention (especially damping and/or restorability) while imparting flexibility. From a viewpoint, it is preferably 2 to 20 parts by mass, more preferably 3 to 18 parts by mass, particularly preferably 4 to 15 parts by mass, based on 100 parts by mass of the thermoplastic elastomer (a).
  • the thermoplastic elastomer composition of the present invention may further contain an inorganic filler within a range that does not impair the effects of the present invention.
  • inorganic fillers those commonly used in this technical field can be used. Examples of inorganic fillers include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate, glass fiber, carbon fiber and the like.
  • the inorganic filler (e) may be used alone or in combination of two or more.
  • the content of the inorganic filler (e) should be On the other hand, it is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and particularly preferably 30 to 100 parts by mass.
  • the thermoplastic elastomer composition may contain other additives as long as they do not impair the effects of the present invention.
  • additives include lubricants, flame retardants, antioxidants, heat stabilizers, light stabilizers, weather stabilizers, metal deactivators, UV absorbers, light stabilizers, copper inhibitors, reinforcing agents, Antistatic agent, antibacterial agent, antifungal agent, dispersant, colorant, polyolefin resin such as polyethylene or polypropylene, isobutylene-isoprene copolymer, rubber such as silicone rubber, ethylene-vinyl acetate copolymer or ABS resin and other thermoplastic resins.
  • Other additives may be used alone or in combination of two or more.
  • the lubricant has the effect of improving the fluidity of the thermoplastic elastomer composition and suppressing thermal deterioration.
  • lubricants include silicone oil; hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, stearyl stearate and the like.
  • flame retardants include phosphorus-based flame retardants such as triphenylphosphine, triallyl phosphate, aromatic phosphate, polyphosphate, red phosphorus, 2-ethylhexyldiphenyl phosphate, and triethyl phosphate; magnesium hydroxide, aluminum hydroxide and other inorganic flame retardants.
  • phosphorus-based flame retardants such as triphenylphosphine, triallyl phosphate, aromatic phosphate, polyphosphate, red phosphorus, 2-ethylhexyldiphenyl phosphate, and triethyl phosphate
  • magnesium hydroxide aluminum hydroxide and other inorganic flame retardants.
  • the content of the additive may be any content that allows the effect of the additive to be exhibited, and can be appropriately selected by those skilled in the art.
  • thermoplastic elastomer composition may be crosslinked, if necessary, as long as the effects of the present invention are not impaired.
  • a radical generator, a cross-linking agent such as sulfur or a sulfur compound may be used, and a cross-linking aid may be used as necessary.
  • radical generators include hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide; di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5 - dialkyl peroxides such as di(t-butylperoxy)-hexyne-3; diacyl peroxides such as acetyl peroxide, succinic acid peroxide, benzoyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl Organic peroxides such as peroxide
  • the radical generator may be used alone or in combination of two or more. When a radical generator is used, it is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, based on a total of 100 parts by mass of the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2). Use within range.
  • An example of a cross-linking method using a radical generator is a method of melt-kneading a thermoplastic elastomer composition and a radical generator under heating.
  • the heating temperature is preferably 140 to 230° C., and the melt-kneading can be carried out batchwise or continuously using devices such as extruders, kneaders, rolls and plastographs.
  • a cross-linking reaction proceeds in this melt-kneading step.
  • sulfur compounds include sulfur monochloride and sulfur dichloride.
  • the amount added is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, based on a total of 100 parts by mass of the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2). 2 to 10 parts by mass.
  • sulfur or a sulfur compound is used for cross-linking, it is extremely preferable to use a vulcanization accelerator as a cross-linking aid.
  • vulcanization accelerators include thiazoles such as N,N-diisopropyl-2-benzothiazole-sulphenamide, 2-mercaptobenzothiazole, 2-(4-morpholinodithio)benzothiazole; diphenylguanidine, triphenyl guanidines such as guanidine; butyraldehyde-aniline reactants, aldehyde-amine reactants or aldehyde-ammonia reactants such as hexamethylenetetramine-acetaldehyde reactants; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethylurea, Thiurams such as dibutylthiourea, trimethylthiourea and diorthotolylthiourea; thiuram monopolysulfides or thiuram polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram
  • the amount added is preferably 0.05 to 30 parts by mass, more preferably 0.05 part by mass, with respect to a total of 100 parts by mass of the thermoplastic elastomer (a1) and the thermoplastic elastomer (a2). 1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.
  • premixing methods include a method using a mixer such as a Henschel mixer, a high speed mixer, a V blender, a ribbon blender, a tumbler blender, and a conical blender.
  • the temperature during melt-kneading can be arbitrarily selected, preferably within the range of 200°C to 300°C.
  • the thermoplastic elastomer composition of the present invention has excellent damping properties, excellent restorability and excellent heat resistance.
  • the damping property can be evaluated, for example, by tan ⁇ at 23°C.
  • the tan ⁇ at 23° C. of the thermoplastic elastomer composition is preferably 0.15 or more, more preferably 0.17 or more, and particularly preferably 0.20 or more.
  • the restorability can be evaluated by elongation set, for example.
  • the elongation set of the thermoplastic elastomer composition is preferably 13% or less, more preferably 10% or less, and particularly preferably 7% or less.
  • Heat resistance can be evaluated, for example, by compression set.
  • the elongation set of the thermoplastic elastomer composition is preferably 50% or less, more preferably 45% or less, and particularly preferably 40% or less.
  • the tan ⁇ at 23° C., the elongation set and the compression set of the thermoplastic elastomer composition can be measured by the methods described in Examples below.
  • thermoplastic elastomer composition Three test pieces with a thickness of 2 mm obtained by injection molding a thermoplastic elastomer composition at 230° C. are stacked, and the hardness obtained after 3 seconds using a type A durometer in accordance with JIS K 6253 is preferably 80 or less. , more preferably 75 or less, still more preferably 70 or less, and particularly preferably 65 or less.
  • the hardness is preferably 15 or higher, more preferably 20 or higher, even more preferably 25 or higher, and particularly preferably 30 or higher.
  • the thermoplastic elastomer composition tends to have an excellent balance between strength and damping properties.
  • thermoplastic elastomer composition of the present invention can be produced by subjecting the thermoplastic elastomer composition of the present invention to molding using a conventionally known molding method such as hot pressing, injection molding, extrusion molding, calender molding, or the like. Accordingly, the present invention also covers moldings made from the thermoplastic elastomer composition of the present invention.
  • the thermoplastic elastomer composition of the present invention has excellent fluidity because the thermoplastic elastomer (a1), which is an essential component, has excellent absorbability of the softening agent (c). Therefore, the thermoplastic elastomer composition of the present invention is excellent in handleability during melt-kneading, and is also excellent in moldability.
  • the molded body can have any shape, for example, a sheet-like, disc-like, or cylindrical shape.
  • the molded body can have any dimensions, the dimensions being determined according to the application.
  • a layer made of a resin composition other than the thermoplastic elastomer composition of the present invention can be bonded to at least part of the surface of the molded article of the present invention.
  • Such layers may be singly or in combination of two or more.
  • thermoplastic elastomer was obtained by performing gel permeation chromatography measurement under the following measurement conditions and converting with standard polystyrene.
  • GPC LC Solution (manufactured by Shimadzu Corporation)
  • Detector Differential refractometer RID-10A (manufactured by Shimadzu Corporation)
  • Column TSKgelG4000Hxl (manufactured by Tosoh Corporation) with two columns joined in series Guard column: TSKguardcolumnHxl-L (manufactured by Tosoh Corporation)
  • Solvent Tetrahydrofuran Temperature: 40°C Flow rate: 1 mL/min Concentration: 2 mg/mL
  • thermoplastic elastomer (2) Content of Structural Unit Derived from Aromatic Vinyl Compound in Thermoplastic Elastomer
  • the thermoplastic elastomer was dissolved in CDCl 3 and 1 H-NMR spectrum was measured (device: JNM-Lambda manufactured by JEOL Ltd.) 500, measurement temperature: 50°C).
  • the content of structural units derived from the aromatic vinyl compound in the thermoplastic elastomer was calculated from the peak area derived from the aromatic vinyl compound.
  • thermoplastic elastomer (3) the total content of 1,2-bonding units and 3,4-bonding units of structural units derived from the conjugated diene compound in the thermoplastic elastomer, and from the structural units derived from the conjugated diene compound in the thermoplastic elastomer; Hydrogenation Rate of Constituent Polymer Block
  • the thermoplastic elastomer was dissolved in CDCl 3 and 1 H-NMR spectrum was measured (device: JNM-Lambda 500 manufactured by JEOL Ltd., measurement temperature: 50° C.).
  • the hydrogenation rate of a polymer block composed of structural units derived from a conjugated diene compound in a thermoplastic elastomer was determined by dissolving the thermoplastic elastomer in CDCl 3 and measuring the 1 H-NMR spectrum (apparatus: "ADVANCE 400 Nano bay” (manufactured by Bruker), measurement temperature: 30 ° C.), all peaks related to double bonds in conjugated diene monomer units in the obtained peaks (1,2-bond, 3,4-bond) ) to the total area of hydrogenated 1,2-bonds and hydrogenated 3,4-bonds (peak area derived from residual olefins of isoprene or butadiene and ethylene, propylene, butylene , peak area ratio derived from 2-methylbutylene and 3-methylbutylene).
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet with a thickness of 2 mm. .
  • Ten ultrathin slices with a thickness of about 150 nm were prepared using a Leica ultramicrotome (model: Ultracut S/FC-S) so that the surface (top or bottom) of the obtained sheet was the observation surface.
  • Each ultra-thin section was placed in a copper mesh. Vapor staining was performed on each ultrathin section using an aqueous RuO4 solution.
  • a transmission electron microscope (model: HT7700, compatible with 3DTEM ) manufactured by Hitachi High-Technologies Corporation equipped with a LaB6 electron gun was used. Morphological observation was performed under the conditions of an acceleration voltage of 100 kV, a LaB6 electron beam dose of 10 ⁇ A, and an electron beam spot size of 1 ⁇ m.
  • a bottom-mount camera manufactured by AMT (model: XR81B, 8-megapixel camera) was used as a CCD camera for photographing and recording. The maximum length of the polyphenylene ether resin (b) in the transmission electron microscope image of each ultrathin section obtained is confirmed, and the polyphenylene ether resin in the transmission electron microscope image of each ultrathin section based on the scale attached to the image.
  • the maximum length of polyphenylene ether resin (b) was obtained, and the maximum length of polyphenylene ether resin (b), which was the largest among them, was adopted as the maximum length of polyphenylene ether resin (b) in the thermoplastic elastomer composition.
  • the structural unit phase derived from the aromatic vinyl compound (polymer block X1 and/or The maximum length of polymer block X2) was adopted as the maximum length of polyphenylene ether resin (b) in the thermoplastic elastomer composition. In that case, it is presumed that the phase of the structural unit derived from the aromatic vinyl compound contains the polyphenylene ether resin (b).
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was compression molded at 200° C. and 1.0 MPa for 3 minutes to obtain a sheet (length 150 mm, width 150 mm, thickness 1 mm).
  • a cylindrical test piece having a diameter of 25 mm and a height of 1 mm was punched from this sheet.
  • Rheometric Scientific's "RDA3 viscoelasticity measuring device" in accordance with JIS K7244-10, the shear storage modulus was measured under the conditions of a measurement temperature of 100 to 350 ° C., a frequency of 1 Hz, and a strain of 5%. G' was measured. In the resulting chart, the temperature at the intersection of the baseline and the tangent to the point where the shear storage modulus G' began to decline was read as the order-disorder transition temperature.
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet with a thickness of 2 mm. Three disc-shaped test pieces with a diameter of 120 mm were produced from the obtained sheet. According to JIS K 6253, the hardness was measured by stacking three test pieces. A type A durometer was used as a hardness tester, and the value after 3 seconds was recorded as the hardness.
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet with a thickness of 2 mm. A disk-shaped test piece with a diameter of 120 mm was produced from the obtained sheet. For the prepared test piece, using a viscoelasticity measurement analyzer (Reogel-E4000 manufactured by UBM Co., Ltd.), at a frequency of 30 Hz and a heating rate of 3 ° C./min, the storage elastic modulus (E') and the loss elastic modulus (E") were measured.
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet with a thickness of 2 mm.
  • a test piece was punched out from the obtained sheet using a No. 1 dumbbell so that the measurement direction was the TD direction, and a 4 cm marked line was drawn.
  • the obtained test piece was stretched 100% for 10 minutes and then allowed to stand for 10 minutes. After that, the distance between gauge lines was measured, and the amount of strain was calculated. The smaller this value, the better the restorability.
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet having a thickness of 2 mm.
  • Six disc-shaped test pieces with a diameter of 120 mm were produced from the obtained sheet.
  • JIS K 6262 6 sheets of the test piece were stacked, and the compression set was measured after holding 25% compression deformation at 70° C. for 22 hours. A smaller value indicates better heat resistance.
  • thermoplastic elastomer composition obtained in Examples and Comparative Examples was molded at 230° C. using an injection molding machine (FE120 manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a sheet with a thickness of 2 mm. A test piece was punched out from the obtained sheet using a No. 3 dumbbell so that the measurement direction was the TD direction. The obtained test piece was stretched by 100% and allowed to stand in an environment of 130°C. The presence or absence of cracks after 8 hours was observed.
  • Thermoplastic elastomer (a1)-1 Preparation of styrene-butadiene-styrene type triblock copolymer Into a pressure vessel that has been purged with nitrogen and dried, 72 L of cyclohexane as a solvent and sec-butyllithium as a polymerization initiator ( 10 mass % cyclohexane solution) was introduced, and 99 g of N,N,N',N'-tetramethylethylenediamine as an organic Lewis base was added.
  • ⁇ Thermoplastic elastomer (a2)-1 Preparation of styrene-isoprene-styrene type triblock copolymer Into a pressure vessel that has been purged with nitrogen and dried, 64 L of cyclohexane as a solvent and sec-butyllithium as a polymerization initiator ( 0.20 L of a 10% by mass cyclohexane solution) was introduced, and 0.3 L of tetrahydrofuran as an organic Lewis base (equivalent to 15 times the stoichiometric ratio with respect to lithium atoms in the polymerization initiator) was added.
  • Weight average molecular weight 100,000 Content of structural units derived from isoprene: 80% by mass Content of structural units derived from styrene: 20% by mass Content of 1,2-bonding units and 3,4-bonding units in structural units derived from isoprene: 60 mol% Hydrogenation rate of polymer block composed of structural units derived from conjugated diene compound: 0% ODTT: 250°C
  • ⁇ Thermoplastic elastomer (a3)-1 Preparation of styrene-isoprene-styrene triblock copolymer 0.20 L of a 10% by mass cyclohexane solution) was introduced, and 0.3 L of tetrahydrofuran as an organic Lewis base (equivalent to 15 times the stoichiometric ratio with respect to lithium atoms in the polymerization initiator) was added. After raising the temperature to 50° C., 2.3 L of styrene was added and polymerized for 3 hours, then 23 L of isoprene was added and polymerized for 4 hours, and 2.3 L of styrene was further added and polymerized for 3 hours.
  • the resulting reaction solution was poured into 80 L of methanol, and the precipitated solid was collected by filtration and dried at 50° C. for 20 hours to obtain a styrene-isoprene-styrene type triblock copolymer.
  • 10 kg of the obtained triblock copolymer was dissolved in 200 L of cyclohexane, and palladium carbon (amount of palladium supported: 5% by mass) was added as a hydrogenation catalyst in an amount of 5% by mass with respect to the copolymer.
  • the reaction was carried out for 10 hours under conditions of a pressure of 2 MPa and a temperature of 150°C. After cooling and pressure release, palladium carbon was removed by filtration.
  • the filtrate was concentrated and dried in vacuum to obtain a hydrogenated styrene-isoprene-styrene type triblock copolymer.
  • the properties of the obtained hydrogenated product were as follows. Weight average molecular weight: 100,000 Content of structural units derived from isoprene: 80% by mass Content of structural units derived from styrene: 20% by mass Content of 1,2-bonding units and 3,4-bonding units in structural units derived from isoprene: 60 mol% Hydrogenation rate of polymer block composed of structural units derived from conjugated diene compound: 98% ODTT: 300°C
  • PPO 640 trade name
  • SABIC Innovative Plastics Japan G.K. softener for rubber
  • Diana Process Oil PW-380 (trade name), manufactured by Idemitsu Kosan Co., Ltd., paraffin oil, kinematic viscosity (40° C.): 381.6 mm 2 /s, ring analysis paraffin: 73%, ring analysis naphthene: 27%, weight Average molecular weight: 1304 ⁇ Polypropylene
  • Prime Polypro J108M trade name
  • Examples 1 to 9 and Comparative Examples 1 to 6 Using a twin-screw extruder (TEM-26SS-P1 manufactured by Toshiba Machine Co., Ltd.), under the conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 200 rpm, each component is melt-kneaded at the blending ratio shown in Tables 1 and 2, and strands are obtained. extruded into a shape. A pelletizer connected to the twin-screw extruder cut the extruded strands to obtain pellets of the thermoplastic elastomer composition.
  • TEM-26SS-P1 manufactured by Toshiba Machine Co., Ltd.
  • thermoplastic elastomer compositions prepared in Example 2 and Comparative Example 3, respectively.
  • thermoplastic elastomer compositions obtained in Examples 1 to 9 are excellent in damping properties, restorability and heat resistance.
  • the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 6 gave low evaluation results in at least one of damping properties, restorability and heat resistance.
  • the polyphenylene ether resin (b) was highly dispersed in the matrix phase, and the polyphenylene ether resin (b) was observed with a transmission electron microscope. It was difficult to distinguish clearly as the polyphenylene ether resin (b) in the image.
  • thermoplastic elastomer composition of the present invention is excellent in damping properties, resilience and heat resistance. Also, the thermoplastic elastomer composition of the present invention has appropriate hardness. Therefore, it can be suitably used as a damping member or the like that is applied for damping vibrations of home electric appliances, automobile parts, sporting goods, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une composition d'élastomère thermoplastique contenant (a) un élastomère thermoplastique, (b) une résine de polyphénylène éther et (c) un agent ramollisseur de caoutchouc, (a) comprenant (a1) et (a2) selon un rapport de masse de 90:10 à 45:55, (a1) étant un copolymère séquencé comprenant une séquence polymère (X1) et une séquence polymère (Y1) et présentant une masse moléculaire moyenne en poids spécifique et une teneur en motifs structuraux dérivés d'un composé vinylique aromatique spécifique ; (a2) étant un copolymère séquencé comprenant une séquence polymère (X2) et une séquence polymère (Y2) et présentant une masse moléculaire moyenne en poids spécifique, une teneur en motifs structuraux dérivés d'un composé vinylique aromatique spécifique et une teneur en liaisons vinyliques spécifique ; le diamètre long maximal de (b) dispersée dans la phase matricielle comprenant (a) étant inférieur ou égal à 2 µm sur une image de la composition prise au microscope électronique en transmission ; et une dureté (A) de la composition conforme à la norme JIS K 6253 étant inférieure ou égale à 80.
PCT/JP2022/027823 2021-07-21 2022-07-15 Composition d'élastomère thermoplastique et corps moulé comprenant ladite composition Ceased WO2023002932A1 (fr)

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WO2025032673A1 (fr) * 2023-08-07 2025-02-13 株式会社タイカ Composition de résine thermoplastique

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JP2010024275A (ja) * 2008-07-16 2010-02-04 Aron Kasei Co Ltd 耐熱制振性エラストマー組成物
WO2015087954A1 (fr) * 2013-12-11 2015-06-18 株式会社クラレ Matériau d'étanchéité
WO2015159912A1 (fr) * 2014-04-16 2015-10-22 旭化成ケミカルズ株式会社 Composition élastomère thermoplastique, bouchon pour récipient médical et récipient médical
JP2017190459A (ja) * 2011-02-14 2017-10-19 株式会社クラレ 熱可塑性エラストマー組成物
WO2018139122A1 (fr) * 2017-01-24 2018-08-02 旭化成株式会社 Composition élastomère thermoplastique, bouchon et récipient
WO2019103048A1 (fr) * 2017-11-22 2019-05-31 株式会社クラレ Copolymère séquencé, et produit hydrogéné de celui-ci
WO2019230872A1 (fr) * 2018-05-31 2019-12-05 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine et différentes applications associées
JP2020019947A (ja) * 2018-07-20 2020-02-06 旭化成株式会社 熱可塑性エラストマー組成物、栓体及び容器

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Publication number Priority date Publication date Assignee Title
WO2008018445A1 (fr) * 2006-08-08 2008-02-14 Asahi Kasei Chemicals Corporation Copolymères séquencés hydrogénés et compositions de réticulation les contenant
JP2010024275A (ja) * 2008-07-16 2010-02-04 Aron Kasei Co Ltd 耐熱制振性エラストマー組成物
JP2017190459A (ja) * 2011-02-14 2017-10-19 株式会社クラレ 熱可塑性エラストマー組成物
WO2015087954A1 (fr) * 2013-12-11 2015-06-18 株式会社クラレ Matériau d'étanchéité
WO2015159912A1 (fr) * 2014-04-16 2015-10-22 旭化成ケミカルズ株式会社 Composition élastomère thermoplastique, bouchon pour récipient médical et récipient médical
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WO2019103048A1 (fr) * 2017-11-22 2019-05-31 株式会社クラレ Copolymère séquencé, et produit hydrogéné de celui-ci
WO2019230872A1 (fr) * 2018-05-31 2019-12-05 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine et différentes applications associées
JP2020019947A (ja) * 2018-07-20 2020-02-06 旭化成株式会社 熱可塑性エラストマー組成物、栓体及び容器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025032673A1 (fr) * 2023-08-07 2025-02-13 株式会社タイカ Composition de résine thermoplastique
WO2025033189A1 (fr) * 2023-08-07 2025-02-13 株式会社タイカ Composition de résine thermoplastique

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