WO2015060201A1 - Thermoplastic elastomer composition - Google Patents

Thermoplastic elastomer composition Download PDF

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Publication number
WO2015060201A1
WO2015060201A1 PCT/JP2014/077610 JP2014077610W WO2015060201A1 WO 2015060201 A1 WO2015060201 A1 WO 2015060201A1 JP 2014077610 W JP2014077610 W JP 2014077610W WO 2015060201 A1 WO2015060201 A1 WO 2015060201A1
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mass
thermoplastic elastomer
parts
elastomer composition
polymer
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PCT/JP2014/077610
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French (fr)
Japanese (ja)
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伸浩 三輪
高山　治幸
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クラレプラスチックス株式会社
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Publication of WO2015060201A1 publication Critical patent/WO2015060201A1/en

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    • 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
    • C08L53/02—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 of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—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 of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • C08L23/12—Polypropene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a thermoplastic elastomer composition.
  • thermoplastic elastomer compositions do not require a vulcanization process and can be molded in the same way as thermoplastic resins, so they can be used in a wide range of fields such as automobile parts, home appliance parts, toys, sports equipment, daily necessities, and sundries. in use.
  • thermoplastic elastomer compositions a thermoplastic elastomer composition using a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound cannot be obtained with other materials by utilizing its excellent oil retention. It is used for a wide range of applications from a very low hardness range to a high hardness range equivalent to polyethylene by utilizing the excellent affinity between polypropylene and polyethylene.
  • Patent Documents 1 and 2 disclose a thermoplastic elastomer composition containing a hydrogenated block copolymer, a polyolefin polymer, and a softening agent.
  • these thermoplastic elastomer compositions are not fully satisfactory in the balance of heat resistance, fluidity, whitening resistance, surface properties, mechanical properties and thin moldability, and further improvements are desired.
  • an object of the present invention is to provide a thermoplastic elastomer composition that is excellent in heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin-wall moldability.
  • a specific hydrogenated block copolymer containing a polymer block composed of an aromatic vinyl compound and a polymer block composed of a conjugated diene compound, and a hydrocarbon rubber softener The present inventors have found that the above-mentioned problems can be solved by blending a specific olefin resin and a silicone oil having a specific kinematic viscosity at a specific ratio.
  • the present invention [1] A 5% by weight toluene solution obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound 100 parts by mass of a hydrogenated block copolymer (A) having a solution viscosity measured at 30 ° C. in the range of 50 to 200 mPa ⁇ s, 150 to 350 parts by mass of a softening agent for hydrocarbon rubber (B), a propylene polymer And olefin resin (C) having an ethylene polymer content of 1 to 20% by mass, and a kinematic viscosity measured at 25 ° C.
  • A hydrogenated block copolymer having a solution viscosity measured at 30 ° C. in the range of 50 to 200 mPa ⁇ s, 150 to 350 parts by mass of a softening agent for hydrocarbon rubber (B), a propylene polymer And olefin
  • thermoplastic elastomer composition containing 0.05 to 3 parts by mass of a silicone oil (D); [2] The thermoplastic elastomer composition according to [1], wherein the conjugated diene compound is at least one selected from isoprene and butadiene; [3] the kinematic viscosity measured at 40 ° C.
  • hydrocarbon softening agent for rubber (B) is less than 100 mm 2 / s [1] or a thermoplastic elastomer composition according to [2]; [4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the hydrocarbon rubber softener (B) has a paraffin content of 73% or more by ring analysis; About.
  • thermoplastic elastomer composition having good heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin moldability.
  • thermoplastic elastomer composition of the present invention is obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound.
  • C hydrocarbon-based rubber softener
  • D silicone oil having a specific kinematic viscosity
  • the hydrogenated block copolymer (A) is obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound. It is obtained.
  • the aromatic vinyl compound include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene and ⁇ -methylstyrene are preferred.
  • An aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.
  • conjugated diene compound examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.
  • a conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.
  • the conjugated diene compound is preferably at least one selected from isoprene and butadiene, and a mixture of isoprene and butadiene is more preferable.
  • the content of the aromatic vinyl compound in the hydrogenated block copolymer (A) is preferably 5 to 75% by mass, more preferably 5 to 50% by mass. When the content of the aromatic vinyl compound is within this range, the rubber elasticity of the thermoplastic elastomer composition of the present invention is further improved.
  • 50% or more of carbon-carbon double bonds derived from the conjugated diene compound of the polymer block (b) are preferably hydrogenated, and 75% or more. More preferably, hydrogenation is performed, and 95% or more is particularly preferable.
  • the hydrogenated block copolymer (A) only needs to contain at least one polymer block (a) and one polymer block (b), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable to contain 2 or more united blocks (a) and 1 or more polymer blocks (b).
  • the bonding mode of the polymer block (a) and the polymer block (b) may be linear, branched or any combination thereof.
  • the polymer block (a) is a, and the polymer block ( When b) is represented by b, a triblock structure represented by aba, (ab) n , (ab) n -a (where n represents an integer of 2 or more) Among them, those having a triblock structure represented by aba are particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
  • the weight average molecular weight of the hydrogenated block copolymer (A) is preferably in the range of 100,000 to 500,000, and more preferably in the range of 150,000 to 450,000 from the viewpoint of moldability.
  • the weight average molecular weight as used in this specification means the weight average molecular weight of standard polystyrene conversion calculated
  • the hydrogenated block copolymer (A) needs to have a solution viscosity measured in a 5% by mass toluene solution at 30 ° C. in the range of 50 to 200 mPa ⁇ s, and a range of 60 to 150 mPa ⁇ s. preferable.
  • a solution viscosity measured in a 5% by mass toluene solution at 30 ° C. in the range of 50 to 200 mPa ⁇ s, and a range of 60 to 150 mPa ⁇ s. preferable.
  • the solution viscosity is within the above range, the tensile strength particularly in mechanical properties can be improved.
  • the solution viscosity is smaller than the above range, the tensile strength becomes insufficient, which is not preferable.
  • hydrocarbon rubber softener (B) examples include process oils such as paraffinic oil, naphthenic oil, and aroma oil, liquid paraffin, and the like. Among them, process oils such as paraffinic oil and naphthenic oil are used. Is preferred. These may be used alone or in combination of two or more.
  • the mass average molecular weight of the hydrocarbon rubber softener (B) is preferably 300 to 2,000. Within this range, when the thermoplastic elastomer composition of the present invention is processed into a molded product, oil bleed is extremely reduced.
  • the hydrocarbon rubber softener (B) preferably has a kinematic viscosity at 40 ° C. of 100 mm 2 / s or less. Although a minimum is not specifically limited, 10 mm ⁇ 2 > / s or more is preferable and 20 mm ⁇ 2 > / s or more is more preferable. If the kinematic viscosity is within this range, a thermoplastic elastomer composition having particularly excellent thin-wall moldability can be obtained. In addition, kinematic viscosity as used in this specification is the value measured according to ASTM D445.
  • the hydrocarbon rubber softener (B) preferably has a paraffin content by ring analysis of 73% or more. Furthermore, the naphthene content by ring analysis is more preferably 27% or less. When the paraffin content and the naphthene content are within the above ranges, a thermoplastic elastomer composition having particularly excellent fluidity can be obtained.
  • the ring analysis referred to in this specification means a method (ndM ring analysis) based on ASTM D3228.
  • the blending amount of the hydrocarbon-based rubber softener (B) is 150 to 350 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (A). Is 170 to 330 parts by mass. If it is less than 150 parts by mass, the fluidity is inferior, and if it exceeds 350 parts by mass, the mechanical properties (tensile strength) are lowered.
  • the olefin resin (C) includes a propylene polymer and an ethylene polymer, and the content of the ethylene polymer is 1 to 20% by mass.
  • the propylene polymer for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used. Among these, it is preferable to use random polypropylene or block polypropylene.
  • ethylene polymer examples include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc.
  • An ethylene / ⁇ -olefin copolymer or the like can be used.
  • propylene polymers and ethylene polymers can be used alone as long as the content of the ethylene polymer contained in the olefin resin (C) is in the range of 1 to 20% by mass. Also, two or more types may be used in combination. When two or more types are used in combination, the total content of the ethylene polymers contained in them may be in the range of 1 to 20% by mass.
  • the melt flow rate (MFR) measured under the conditions of 230 ° C. and 21 N of the propylene polymer is preferably 20 g / 10 minutes or more.
  • the melt flow rate (MFR) measured under the conditions of 190 ° C. and 21 N of the ethylene polymer is preferably 10 g / 10 min or more. If the MFR is too small, the molding processability of the thermoplastic elastomer composition tends to decrease.
  • the MFR can be measured according to JIS K 7210.
  • the olefin-based resin (C) used in the present invention includes a propylene-based polymer and an ethylene-based polymer from the viewpoint of good fluidity and whitening resistance of the obtained thermoplastic elastomer composition, and the ethylene-based resin. It is necessary that the content of the polymer is in the range of 1 to 20% by mass. The content of the ethylene polymer is preferably in the range of 2 to 18% by mass. When the content of the ethylene polymer is 1% by mass or more, the thin-wall moldability and the whitening resistance are further improved. When the ethylene polymer content is 20% by mass or less, a thermoplastic elastomer composition excellent in mechanical properties (tensile strength, elongation at break), thin moldability and whitening resistance is obtained.
  • the blending amount of the olefin resin (C) is 150 to 350 parts by weight, preferably 190 to 330 parts by weight based on 100 parts by weight of the hydrogenated block copolymer (A). Part by mass. If it is less than 150 parts by mass, the fluidity is inferior, and if it exceeds 350 parts by mass, the mechanical properties (tensile strength) are lowered.
  • the silicone oil (D) has a kinematic viscosity measured at 25 ° C. of 200 mm 2 / s or less.
  • a high viscosity product having a kinematic viscosity exceeding 200 mm 2 / s has a large molecular weight and cannot improve the surface properties of the thermoplastic elastomer composition.
  • the kinematic viscosity of the silicone oil (D) is more preferably 100 mm 2 / s or less, and still more preferably 50 mm 2 / s or less.
  • the lower limit is not particularly limited, but those having a very low kinematic viscosity cause bleed-out on the surface of the molded skin and are not preferable in appearance, and are therefore preferably 0.1 mm 2 / s or more, more preferably 1 mm 2 / s or more.
  • silicone oil (D) for example, dimethyl silicone oil, methylphenyl silicone oil or the like can be used. These may be used alone or in combination of two or more.
  • the silicone oil (D) is blended in an amount of 0.05 to 3 parts by weight, preferably 0.003 parts per 100 parts by weight of the hydrogenated block copolymer (A). 1 to 0.5 parts by mass. If the amount is less than 0.05 parts by mass, the effect of improving the surface tackiness is inferior. If the amount exceeds 3 parts by mass, bleeding occurs and the appearance is inferior.
  • thermoplastic elastomer composition of the present invention includes various anti-blocking agents, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, foaming depending on the application. It is also possible to contain a coloring agent, a coloring agent and the like.
  • antioxidants for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 -Bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro-5, Phenolic antioxidants such as 5-undecane, phosphite antioxidants, thioether antioxidants, and the like can be used.
  • the antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the components (A) to (D) contained in the thermoplastic elastomer composition of the present invention. More preferably, the content is 0.05 to 1.0 part by mass.
  • thermoplastic elastomer composition As a method for producing the thermoplastic elastomer composition of the present invention, a method used for producing a normal resin composition or a rubber composition can be employed. A single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll It can be produced by uniformly mixing the components using a melt kneader such as various kneaders. The set temperature of the processing machine can be arbitrarily selected from 150 ° C to 300 ° C. The hardness of the thermoplastic elastomer composition is preferably adjusted so as to be 20 to 50 in the JIS D type.
  • thermoplastic elastomer composition of the present invention can be obtained by using various molding methods, for example, extrusion molding, injection molding, hollow molding, compression molding, calendar molding, or any other method such as sheet, film, and tube. It can be formed into a shaped molded body. Moreover, the thermoplastic elastomer composition of the present invention can also be made into a composite molded body formed by compounding with other materials such as plastics and fabrics by two-color molding method, insert molding method, co-extrusion and the like.
  • thermoplastic elastomer composition of the present invention can be used as a raw material for various industrial products and industrial parts.
  • automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, and airbag covers
  • automotive exterior parts such as malls
  • remote control switches and various key tops for OA equipment Home appliance parts such as TVs, stereos, vacuum cleaners, etc .
  • underwater products such as underwater glasses and underwater camera covers; various cover parts; industry with various packing for sealing, waterproofing, soundproofing, vibration-proofing, etc.
  • Automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc .
  • Electrical and electronic parts such as wire coverings
  • Footwear applications such as sports shoes and fashion sandals
  • Building materials such as window frame materials; various joints; used for valve parts, etc. It can be.
  • Hardness A sheet having a thickness of 2 mm was obtained by injection molding the thermoplastic elastomer compositions obtained in Examples and Comparative Examples at 230 ° C. Using this sheet, the JIS-D hardness was measured in accordance with JIS K 6253.
  • MFR Using the thermoplastic elastomer compositions obtained in Examples and Comparative Examples, MFR (g / 10 min) under a load condition of 190 ° C. and 21 N was measured according to JIS K 7210, and used as an index of flow characteristics. .
  • Breaking strength and breaking elongation The thermoplastic elastomer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a thickness of 2 mm.
  • thermoplastic elastomer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a thickness of 2 mm. Then, an angle-shaped test piece without incision was punched out, a tear test was performed according to JIS K 6252, and the tear strength was measured.
  • thermoplastic elastomer compositions obtained in the examples and comparative examples were injection-molded into a mold having a thickness of 0.5 mm and a width of 40 mm at 230 ° C., and delamination and flow marks near the gate.
  • the appearance defects such as short shots were observed and used as indicators of thin-wall moldability ( ⁇ : very good, ⁇ : good, ⁇ : slightly defective, ⁇ : defective).
  • Surface property The injection-molded sheet of the thermoplastic polymer composition obtained in the examples and comparative examples was traced with a fingertip to obtain an index of surface property (no stickiness: ⁇ , with stickiness: x).
  • ⁇ Softener for hydrocarbon rubber (B)> ⁇ Ingredient (b-1) Diana Process Oil PW90 (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., paraffinic oil, kinematic viscosity (40 ° C.): 95.5 mm 2 / s, ring analysis paraffin: 71%, ring analysis naphthene: 29% ⁇ Ingredient (b-2) KixxPO8 (trade name), manufactured by GS Caltex Corporation, paraffinic oil, kinematic viscosity (40 ° C.): 49.4 mm 2 / s, ring analysis paraffin: 79%, ring analysis naphthene: 21%
  • Ingredient (c-1) Prime polypropylene J708UG (trade name), manufactured by Prime Polymer Co., Ltd., block polypropylene, MFR (230 ° C., 21.18 N): 45 g / 10 min, ethylene polymer content: 14% by mass ⁇
  • Ingredient (c-2) Prime polypropylene J108M (trade name), manufactured by Prime Polymer Co., Ltd., homopolypropylene, MFR (230 ° C., 21.18N): 45 g / 10 min, ethylene polymer content: 0% by mass ⁇
  • Ingredient (c-3) Novatec Polyethylene LJ8041 (trade name), manufactured by Nippon Polypropylene Co., Ltd., low density polyethylene (LDPE), MFR (190 ° C., 21.18 N): 23 g / 10 minutes, ethylene polymer content: 100% by mass.
  • LDPE low density polyethylene
  • Ingredient (d-1) Dimethyl silicone oil AK35 (trade name), Asahi Kasei Wacker Silicone Co., kinematic viscosity (25 °C): 35mm 2 / s ⁇
  • Ingredient (d-2) Dimethyl silicone oil AK350 (trade name), manufactured by Asahi Kasei Wacker Silicone Co., Ltd., kinematic viscosity (25 ° C.): 350 mm 2 / s
  • thermoplastic elastomer composition No. 4 exhibits good heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin moldability.
  • the content of the ethylene polymer in the olefin resin (C) exceeds 20% by mass, so mechanical properties (tensile strength, elongation at break) ), Poor fluidity, whitening resistance, and thin-wall formability.
  • thermoplastic elastomer composition of Comparative Example 3 uses a hydrogenated block copolymer having a solution viscosity of less than 50 mPa ⁇ s and outside the scope of the present invention, it is inferior in mechanical properties (tensile strength) and whitening resistance.
  • the thermoplastic elastomer compositions of Comparative Examples 4 and 5 use a hydrogenated block copolymer having a solution viscosity of less than 50 mPa ⁇ s and outside the scope of the present invention, and an ethylene polymer in the olefin resin (C). Is more than 20% by mass, it is inferior in mechanical properties (tensile strength, elongation at break), fluidity, whitening resistance, and thin-wall moldability.
  • thermoplastic elastomer composition of Comparative Example 6 is inferior in whitening resistance and thin-wall moldability because the olefin resin (C) does not contain an ethylene polymer.
  • the thermoplastic elastomer composition of Comparative Example 7 has poor surface properties because the viscosity of the silicone oil (D) exceeds 350 mm 2 / s. Since Comparative Example 8 is polyethylene alone, it has poor mechanical properties (tensile strength, elongation at break) and heat resistance.
  • thermoplastic elastomer composition of the present invention is excellent in heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin-wall moldability, so that it can be used for automobile interior materials, exterior materials, floor materials, home appliance parts, foods, etc. It can be used effectively in a wide range of applications such as parts for appliances, audio equipment, OA equipment, various switches, optical cables, sports equipment, shoes, building materials, toys, stationery, and the like.

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Abstract

[Problem] To provide a thermoplastic elastomer composition having excellent heat resistance, fluidability, blushing resistance, surface properties, mechanical properties and thin film formability. [Solution] The problem can be solved by a thermoplastic elastomer composition comprising: 100 parts by mass of a hydrogenated block copolymer (A) which is produced by the hydrogenation of a block copolymer that comprises a polymer block (a) comprising an aromatic vinyl compound and a polymer block (b) comprising a conjugated diene compound, and which has a solution viscosity falling within the range from 50 to 200 mPa·s as measured in a 5 mass% toluene solution at 30°C; 150 to 350 parts by mass of a softening agent for hydrocarbon-type rubbers (B); 150 to 350 parts by mass of an olefin resin (C) which comprises a propylene-type polymer and an ethylene-type polymer, wherein the content of the ethylene-type polymer is 1 to 20% by mass; and 0.05 to 3 parts by mass of a silicone oil (D) which has a kinematic viscosity of 200 mm2/s or less as measured at 25°C.

Description

熱可塑性エラストマー組成物Thermoplastic elastomer composition
　本発明は熱可塑性エラストマー組成物に関する。 The present invention relates to a thermoplastic elastomer composition.
　熱可塑性エラストマー組成物は、加硫工程を必要とせず、熱可塑性樹脂と同様に成形加工が可能であることから、自動車部品、家電製品部品、玩具、スポーツ用品、日用品、雑貨などの広い分野で使用されている。熱可塑性エラストマー組成物の中でも、芳香族ビニル化合物―共役ジエン化合物の水添ブロック共重合体を用いた熱可塑性エラストマー組成物は、その優れたオイル保持性を利用して他種材料では得られない超低硬度領域から、ポリプロピレンとポリエチレンとの優れた親和性を利用して、ポリエチレンと同等の高硬度領域まで、幅広い硬度領域で広範な用途に使用される。例えば、特許文献１及び２には、水添ブロック共重合体、ポリオレフィン系重合体及び軟化剤を含有する熱可塑性エラストマー組成物が開示されている。
　しかし、これらの熱可塑性エラストマー組成物は、耐熱性、流動性、耐白化性、表面性、力学物性及び薄肉成形性のバランスにおいて十分に満足できるものではなく、更なる改善が望まれている。 Thermoplastic elastomer compositions do not require a vulcanization process and can be molded in the same way as thermoplastic resins, so they can be used in a wide range of fields such as automobile parts, home appliance parts, toys, sports equipment, daily necessities, and sundries. in use. Among thermoplastic elastomer compositions, a thermoplastic elastomer composition using a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound cannot be obtained with other materials by utilizing its excellent oil retention. It is used for a wide range of applications from a very low hardness range to a high hardness range equivalent to polyethylene by utilizing the excellent affinity between polypropylene and polyethylene. For example, Patent Documents 1 and 2 disclose a thermoplastic elastomer composition containing a hydrogenated block copolymer, a polyolefin polymer, and a softening agent.
However, these thermoplastic elastomer compositions are not fully satisfactory in the balance of heat resistance, fluidity, whitening resistance, surface properties, mechanical properties and thin moldability, and further improvements are desired.
特許第３７００５１５号公報Japanese Patent No. 3700515 特開２００８－２６４２４２号公報JP 2008-264242 A
　しかして、本発明の目的は、耐熱性、流動性、耐白化性、表面性、力学物性及び薄肉成形性に優れる熱可塑性エラストマー組成物を提供することにある。 Therefore, an object of the present invention is to provide a thermoplastic elastomer composition that is excellent in heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin-wall moldability.
　本発明者らが鋭意検討した結果、芳香族ビニル化合物からなる重合体ブロックと、共役ジエン化合物からなる重合体ブロックとを含有する特定の水添ブロック共重合体と、炭化水素系ゴム用軟化剤、特定のオレフィン系樹脂及び特定の動粘度のシリコーンオイルを特定の割合で配合させることにより、上記課題を解決できることを見出し本発明に至った。 As a result of intensive studies by the present inventors, a specific hydrogenated block copolymer containing a polymer block composed of an aromatic vinyl compound and a polymer block composed of a conjugated diene compound, and a hydrocarbon rubber softener The present inventors have found that the above-mentioned problems can be solved by blending a specific olefin resin and a silicone oil having a specific kinematic viscosity at a specific ratio.
　すなわち、本発明は、
［１］芳香族ビニル化合物からなる重合体ブロック（ａ）と、共役ジエン化合物からなる重合体ブロック（ｂ）とを含有するブロック共重合体を水素添加して得られ、５質量％トルエン溶液において３０℃で測定した溶液粘度が５０～２００ｍＰａ・ｓの範囲にある水添ブロック共重合体（Ａ）１００質量部、炭化水素系ゴム用軟化剤（Ｂ）１５０～３５０質量部、プロピレン系重合体とエチレン系重合体を含み、エチレン系重合体の含有量が１～２０質量％であるオレフィン系樹脂（Ｃ）１５０～３５０質量部、及び２５℃で測定した動粘度が２００ｍｍ２/ｓ以下であるシリコーンオイル（Ｄ）０．０５～３質量部を含有する熱可塑性エラストマー組成物；
［２］前記共役ジエン化合物がイソプレン及びブタジエンから選ばれる少なくとも１種である［１］に記載の熱可塑性エラストマー組成物；
［３］前記炭化水素系ゴム用軟化剤（Ｂ）の４０℃で測定した動粘度が１００ｍｍ２/ｓ以下である［１］又は［２］に記載の熱可塑性エラストマー組成物；
［４］前記炭化水素系ゴム用軟化剤（Ｂ）は、環分析によるパラフィン含有量が７３％以上である［１］～［３］のいずれかに記載の熱可塑性エラストマー組成物；
に関する。 That is, the present invention
[1] A 5% by weight toluene solution obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound 100 parts by mass of a hydrogenated block copolymer (A) having a solution viscosity measured at 30 ° C. in the range of 50 to 200 mPa · s, 150 to 350 parts by mass of a softening agent for hydrocarbon rubber (B), a propylene polymer And olefin resin (C) having an ethylene polymer content of 1 to 20% by mass, and a kinematic viscosity measured at 25 ° C. of 200 mm 2 / s or less. A thermoplastic elastomer composition containing 0.05 to 3 parts by mass of a silicone oil (D);
[2] The thermoplastic elastomer composition according to [1], wherein the conjugated diene compound is at least one selected from isoprene and butadiene;
[3] the kinematic viscosity measured at 40 ° C. hydrocarbon softening agent for rubber (B) is less than 100 mm 2 / s [1] or a thermoplastic elastomer composition according to [2];
[4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the hydrocarbon rubber softener (B) has a paraffin content of 73% or more by ring analysis;
About.
　本発明によれば、良好な耐熱性、流動性、耐白化性、表面性、力学物性及び薄肉成形性を有する熱可塑性エラストマー組成物を提供できる。 According to the present invention, it is possible to provide a thermoplastic elastomer composition having good heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin moldability.
　本発明の熱可塑性エラストマー組成物は、芳香族ビニル化合物からなる重合体ブロック（ａ）と、共役ジエン化合物からなる重合体ブロック（ｂ）とを含有するブロック共重合体を水素添加して得られ、５質量％トルエン溶液において３０℃で測定した溶液粘度が５０～２００ｍＰａ・ｓの範囲にある水添ブロック共重合体（Ａ）、炭化水素系ゴム用軟化剤（Ｂ）、特定のオレフィン系樹脂（Ｃ）及び特定の動粘度のシリコーンオイル（Ｄ）を含有する。 The thermoplastic elastomer composition of the present invention is obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound. Hydrogenated block copolymer (A), hydrocarbon-based rubber softener (B), and specific olefinic resin having a solution viscosity measured in a 5% by mass toluene solution at 30 ° C. in the range of 50 to 200 mPa · s. (C) and a silicone oil (D) having a specific kinematic viscosity are contained.
＜水添ブロック共重合体（Ａ）＞
　前記水添ブロック共重合体（Ａ）は、芳香族ビニル化合物からなる重合体ブロック（ａ）と、共役ジエン化合物からなる重合体ブロック（ｂ）とを含有するブロック共重合体を水素添加して得られるものである。
　前記芳香族ビニル化合物としては、例えばスチレン、α－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、１，３－ジメチルスチレン、ビニルナフタレン、ビニルアントラセン等が挙げられる。これらの中でも、スチレンおよびα－メチルスチレンが好ましい。芳香族ビニル化合物は１種を単独で用いてもよく、２種類以上を併用してもよい。 <Hydrogenated block copolymer (A)>
The hydrogenated block copolymer (A) is obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound. It is obtained.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene and α-methylstyrene are preferred. An aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.
　前記共役ジエン化合物としては、例えばブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、１，３－ヘキサジエン等が挙げられる。共役ジエン化合物は１種を単独で用いてもよく、２種類以上を併用してもよい。これらの中でも、前記共役ジエン化合物がイソプレン及びブタジエンから選ばれる少なくとも１種であることが好ましく、イソプレンとブタジエンの混合物がより好ましい。 Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. A conjugated diene compound may be used individually by 1 type, and may use 2 or more types together. Among these, the conjugated diene compound is preferably at least one selected from isoprene and butadiene, and a mixture of isoprene and butadiene is more preferable.
　前記水添ブロック共重合体（Ａ）における芳香族ビニル化合物の含有量は５～７５質量％が好ましく、５～５０質量％がより好ましい。芳香族ビニル化合物の含有量がこの範囲内であると、本発明の熱可塑性エラストマー組成物のゴム弾性がより向上する。 The content of the aromatic vinyl compound in the hydrogenated block copolymer (A) is preferably 5 to 75% by mass, more preferably 5 to 50% by mass. When the content of the aromatic vinyl compound is within this range, the rubber elasticity of the thermoplastic elastomer composition of the present invention is further improved.
　前記水添ブロック共重合体（Ａ）は、前記重合体ブロック（ｂ）の共役ジエン化合物に由来する炭素－炭素二重結合の５０％以上が水素添加されていることが好ましく、７５％以上が水素添加されていることがより好ましく、９５％以上が水素添加されていることが特に好ましい。 In the hydrogenated block copolymer (A), 50% or more of carbon-carbon double bonds derived from the conjugated diene compound of the polymer block (b) are preferably hydrogenated, and 75% or more. More preferably, hydrogenation is performed, and 95% or more is particularly preferable.
　前記水添ブロック共重合体（Ａ）は、重合体ブロック（ａ）と重合体ブロック（ｂ）とをそれぞれ少なくとも１個含有していればよいが、耐熱性、力学物性等の観点から、重合体ブロック（ａ）を２個以上、重合体ブロック（ｂ）を１個以上含有していることが好ましい。重合体ブロック（ａ）と重合体ブロック（ｂ）の結合様式は、線状、分岐状あるいはこれらの任意の組み合わせであってもよいが、重合体ブロック（ａ）をａで、重合体ブロック（ｂ）をｂで表したとき、ａ－ｂ－ａで示されるトリブロック構造や、（ａ－ｂ）ｎ、（ａ－ｂ）ｎ－ａ、（ここでｎは２以上の整数を表す）で示されるマルチブロック共重合体などを挙げることができ、これらの中でも、ａ－ｂ－ａで示されるトリブロック構造のものが、耐熱性、力学物性、取り扱い性等の点で特に好ましい。 The hydrogenated block copolymer (A) only needs to contain at least one polymer block (a) and one polymer block (b), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable to contain 2 or more united blocks (a) and 1 or more polymer blocks (b). The bonding mode of the polymer block (a) and the polymer block (b) may be linear, branched or any combination thereof. The polymer block (a) is a, and the polymer block ( When b) is represented by b, a triblock structure represented by aba, (ab) n , (ab) n -a (where n represents an integer of 2 or more) Among them, those having a triblock structure represented by aba are particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
　前記水添ブロック共重合体（Ａ）の重量平均分子量は１０万～５０万の範囲内が好ましく、成形加工性等の観点から１５万～４５万の範囲内がより好ましい。なお、本明細書でいう重量平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によって求めた標準ポリスチレン換算の重量平均分子量をいう。 The weight average molecular weight of the hydrogenated block copolymer (A) is preferably in the range of 100,000 to 500,000, and more preferably in the range of 150,000 to 450,000 from the viewpoint of moldability. In addition, the weight average molecular weight as used in this specification means the weight average molecular weight of standard polystyrene conversion calculated | required by the gel permeation chromatography (GPC) measurement.
　前記水添ブロック共重合体（Ａ）は、５質量％トルエン溶液において３０℃で測定された溶液粘度が５０～２００ｍＰａ・ｓの範囲にあることが必要であり、６０～１５０ｍＰａ・ｓの範囲が好ましい。溶液粘度が前記範囲内であると、特に力学物性における引張強さを向上させることができる。溶液粘度が前記範囲より小さい場合には、引張強さが不十分となるため好ましくない。 The hydrogenated block copolymer (A) needs to have a solution viscosity measured in a 5% by mass toluene solution at 30 ° C. in the range of 50 to 200 mPa · s, and a range of 60 to 150 mPa · s. preferable. When the solution viscosity is within the above range, the tensile strength particularly in mechanical properties can be improved. When the solution viscosity is smaller than the above range, the tensile strength becomes insufficient, which is not preferable.
＜炭化水素系ゴム用軟化剤（Ｂ）＞
　前記炭化水素系ゴム用軟化剤（Ｂ）としては、例えばパラフィン系オイル、ナフテン系オイル、アロマ系オイル等のプロセスオイル、流動パラフィン等が挙げられ、中でもパラフィン系オイル、ナフテン系オイル等のプロセスオイルが好ましい。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 <Softener for hydrocarbon rubber (B)>
Examples of the hydrocarbon rubber softener (B) include process oils such as paraffinic oil, naphthenic oil, and aroma oil, liquid paraffin, and the like. Among them, process oils such as paraffinic oil and naphthenic oil are used. Is preferred. These may be used alone or in combination of two or more.
　炭化水素系ゴム用軟化剤（Ｂ）の質量平均分子量は３００～２０００が好ましい。この範囲内であれば、本発明の熱可塑性エラストマー組成物を成形品に加工した際に、オイルのブリードが極めて少なくなる。また、炭化水素系ゴム用軟化剤（Ｂ）は、その４０℃における動粘度が１００ｍｍ２/ｓ以下であるものが好ましい。下限は特に限定されないが、１０ｍｍ２/ｓ以上が好ましく、２０ｍｍ２/ｓ以上がより好ましい。動粘度が当該範囲内であれば、特に薄肉成形性に優れる熱可塑性エラストマー組成物が得られる。なお、本明細書でいう動粘度とはＡＳＴＭ　Ｄ４４５に準じて測定した値である。 The mass average molecular weight of the hydrocarbon rubber softener (B) is preferably 300 to 2,000. Within this range, when the thermoplastic elastomer composition of the present invention is processed into a molded product, oil bleed is extremely reduced. The hydrocarbon rubber softener (B) preferably has a kinematic viscosity at 40 ° C. of 100 mm 2 / s or less. Although a minimum is not specifically limited, 10 mm < 2 > / s or more is preferable and 20 mm < 2 > / s or more is more preferable. If the kinematic viscosity is within this range, a thermoplastic elastomer composition having particularly excellent thin-wall moldability can be obtained. In addition, kinematic viscosity as used in this specification is the value measured according to ASTM D445.
　前記炭化水素系ゴム用軟化剤（Ｂ）は、環分析によるパラフィン含有量が７３％以上であるものが好ましい。さらに、環分析によるナフテン含有量が２７％以下であるものがより好ましい。パラフィン含有量及びナフテン含有量が前記範囲内であることにより、特に流動性に優れる熱可塑性エラストマー組成物が得られる。なお、本明細書でいう環分析とはＡＳＴＭ　Ｄ３２２８に準拠した方法（ｎ－ｄ－Ｍ環分析）を意味する。 The hydrocarbon rubber softener (B) preferably has a paraffin content by ring analysis of 73% or more. Furthermore, the naphthene content by ring analysis is more preferably 27% or less. When the paraffin content and the naphthene content are within the above ranges, a thermoplastic elastomer composition having particularly excellent fluidity can be obtained. The ring analysis referred to in this specification means a method (ndM ring analysis) based on ASTM D3228.
　本発明の熱可塑性エラストマー組成物において、炭化水素系ゴム用軟化剤（Ｂ）の配合量は、水添ブロック共重合体（Ａ）１００質量部に対して１５０～３５０質量部であり、好適には１７０～３３０質量部である。１５０質量部未満では流動性が劣り、３５０質量部を超えると力学物性（引張強さ）が低下する。 In the thermoplastic elastomer composition of the present invention, the blending amount of the hydrocarbon-based rubber softener (B) is 150 to 350 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (A). Is 170 to 330 parts by mass. If it is less than 150 parts by mass, the fluidity is inferior, and if it exceeds 350 parts by mass, the mechanical properties (tensile strength) are lowered.
＜オレフィン系樹脂（Ｃ）＞
　前記オレフィン系樹脂（Ｃ）は、プロピレン系重合体とエチレン系重合体を含み、エチレン系重合体の含有量が１～２０質量％である。プロピレン系重合体としては、例えばホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレン、アタクチックポリプロピレン、シンジオタクチックポリプロピレン等を使用することができる。中でも、ランダムポリプロピレン、ブロックポリプロピレンを用いるのが好ましい。エチレン系重合体としては、例えば中密度ポリエチレン、低密度ポリエチレン（ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のエチレン単独重合体；エチレン・１－ブテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－ヘプテン共重合体、エチレン・１－オクテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・１－ノネン共重合体、エチレン・１－デセン共重合体等のエチレン・α－オレフィン共重合体等を使用することができる。これらのプロピレン系重合体とエチレン系重合体は、オレフィン系樹脂（Ｃ）に含まれるエチレン系重合体の含有量が１～２０質量％の範囲内である限り、１種類を単独で使用しても、２種類以上を併用してもよい。２種類以上を併用する場合は、それらに含まれるエチレン系重合体の含有量の合計が１～２０質量％の範囲内であればよい。 <Olefin resin (C)>
The olefin resin (C) includes a propylene polymer and an ethylene polymer, and the content of the ethylene polymer is 1 to 20% by mass. As the propylene polymer, for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used. Among these, it is preferable to use random polypropylene or block polypropylene. Examples of the ethylene polymer include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc. An ethylene / α-olefin copolymer or the like can be used. These propylene polymers and ethylene polymers can be used alone as long as the content of the ethylene polymer contained in the olefin resin (C) is in the range of 1 to 20% by mass. Also, two or more types may be used in combination. When two or more types are used in combination, the total content of the ethylene polymers contained in them may be in the range of 1 to 20% by mass.
　上記のプロピレン系重合体の２３０℃、２１Ｎの条件下で測定されるメルトフローレート（ＭＦＲ）は、２０ｇ／１０分以上であることが好ましい。ＭＦＲが小さすぎると、熱可塑性エラストマー組成物の成形加工性が低下する傾向がある。 The melt flow rate (MFR) measured under the conditions of 230 ° C. and 21 N of the propylene polymer is preferably 20 g / 10 minutes or more. When MFR is too small, there exists a tendency for the moldability of a thermoplastic elastomer composition to fall.
　上記のエチレン系重合体の１９０℃、２１Ｎの条件下で測定されるメルトフローレート（ＭＦＲ）は、１０ｇ／１０分以上であることが好ましい。ＭＦＲが小さすぎると熱可塑性エラストマー組成物の成形加工性が低下する傾向がある。なお、当該ＭＦＲは、ＪＩＳ　Ｋ　７２１０に準拠して測定することができる。 The melt flow rate (MFR) measured under the conditions of 190 ° C. and 21 N of the ethylene polymer is preferably 10 g / 10 min or more. If the MFR is too small, the molding processability of the thermoplastic elastomer composition tends to decrease. The MFR can be measured according to JIS K 7210.
　本発明で用いられるオレフィン系樹脂（Ｃ）は、得られる熱可塑性エラストマー組成物の良好な流動性、耐白化性等の観点から、プロピレン系重合体とエチレン系重合体とを含み、そのエチレン系重合体の含有量が１～２０質量％の範囲内であることが必要である。エチレン系重合体の含有量は２～１８質量％の範囲内が好ましい。エチレン系重合体の含有量が１質量％以上である場合、薄肉成形性及び耐白化性がより向上する。またエチレン系重合体の含有量が２０質量％以下であると、力学物性（引張強さ、切断時伸び）、薄肉成形性及び耐白化性により優れた熱可塑性エラストマー組成物となる。 The olefin-based resin (C) used in the present invention includes a propylene-based polymer and an ethylene-based polymer from the viewpoint of good fluidity and whitening resistance of the obtained thermoplastic elastomer composition, and the ethylene-based resin. It is necessary that the content of the polymer is in the range of 1 to 20% by mass. The content of the ethylene polymer is preferably in the range of 2 to 18% by mass. When the content of the ethylene polymer is 1% by mass or more, the thin-wall moldability and the whitening resistance are further improved. When the ethylene polymer content is 20% by mass or less, a thermoplastic elastomer composition excellent in mechanical properties (tensile strength, elongation at break), thin moldability and whitening resistance is obtained.
　本発明の熱可塑性エラストマー組成物において、オレフィン系樹脂（Ｃ）の配合量は、水添ブロック共重合体（Ａ）１００質量部に対して１５０～３５０質量部であり、好適には１９０～３３０質量部である。１５０質量部未満では流動性が劣り、３５０質量部を超えると力学物性（引張強さ）が低下する。 In the thermoplastic elastomer composition of the present invention, the blending amount of the olefin resin (C) is 150 to 350 parts by weight, preferably 190 to 330 parts by weight based on 100 parts by weight of the hydrogenated block copolymer (A). Part by mass. If it is less than 150 parts by mass, the fluidity is inferior, and if it exceeds 350 parts by mass, the mechanical properties (tensile strength) are lowered.
＜シリコーンオイル（Ｄ）＞
　前記シリコーンオイル（Ｄ）は、２５℃で測定した動粘度が２００ｍｍ２/ｓ以下である。動粘度が２００ｍｍ２/ｓを超える高粘度品は分子量が大きく、熱可塑性エラストマー組成物の表面性を改良することができない。シリコーンオイル（Ｄ）の動粘度は、より好ましくは１００ｍｍ２/ｓ以下であり、更に好ましくは５０ｍｍ２/ｓ以下である。下限は特に限定されないが、あまりに動粘度が低いものは成形表皮表面にブリードアウトを引き起こし外観上好ましくないため、０．１ｍｍ２/ｓ以上が好ましく、１ｍｍ２/ｓ以上がより好ましい。 <Silicone oil (D)>
The silicone oil (D) has a kinematic viscosity measured at 25 ° C. of 200 mm 2 / s or less. A high viscosity product having a kinematic viscosity exceeding 200 mm 2 / s has a large molecular weight and cannot improve the surface properties of the thermoplastic elastomer composition. The kinematic viscosity of the silicone oil (D) is more preferably 100 mm 2 / s or less, and still more preferably 50 mm 2 / s or less. The lower limit is not particularly limited, but those having a very low kinematic viscosity cause bleed-out on the surface of the molded skin and are not preferable in appearance, and are therefore preferably 0.1 mm 2 / s or more, more preferably 1 mm 2 / s or more.
　前記シリコーンオイル（Ｄ）としては、例えばジメチルシリコーンオイル、メチルフェニルシリコーンオイル等を使用することができる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 As the silicone oil (D), for example, dimethyl silicone oil, methylphenyl silicone oil or the like can be used. These may be used alone or in combination of two or more.
　本発明の熱可塑性エラストマー組成物において、シリコーンオイル（Ｄ）の配合量は、水添ブロック共重合体（Ａ）１００質量部に対して０．０５～３質量部であり、好適には０．１～０．５質量部である。０．０５質量部未満では表面性のべとつき改善効果が劣り、３質量部を超えるとブリードが発生し、外観性に劣る。 In the thermoplastic elastomer composition of the present invention, the silicone oil (D) is blended in an amount of 0.05 to 3 parts by weight, preferably 0.003 parts per 100 parts by weight of the hydrogenated block copolymer (A). 1 to 0.5 parts by mass. If the amount is less than 0.05 parts by mass, the effect of improving the surface tackiness is inferior. If the amount exceeds 3 parts by mass, bleeding occurs and the appearance is inferior.
＜その他の成分＞
　本発明の熱可塑性エラストマー組成物は、上記の成分の他に、用途に応じて各種のブロッキング防止剤、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、滑剤、結晶核剤、発泡剤、着色剤等を含有することも可能である。ここで、酸化防止剤としては、例えば、２,６－ジｔｅｒｔ－ブチル－ｐ－クレゾール、２,６－ジｔｅｒｔ－ブチルフェノール、２,４－ジメチル－６－ｔｅｒｔ－ブチルフェノール、４,４’－ジヒドロキシジフェニル、トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、テトラキス［メチレン－３－（３,５－ジｔｅｒｔ－ブチル－4－ヒドロキシフェニル）プロピオネート］メタン、３,９－ビス｛２－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］－１,１－ジメチルエチル｝－２,４,８,１０－テトラオキサスピロ－５,５－ウンデカンなどのフェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等を使用することができる。中でもフェノール系酸化防止剤、ホスファイト系酸化防止剤が特に好ましい。酸化防止剤は、本発明の熱可塑性エラストマー組成物に含まれる上記成分（Ａ）～（Ｄ）の合計１００質量部に対して、０．０１～３．０質量部であることが好ましく、０．０５～１．０質量部であることがより好ましい。 <Other ingredients>
In addition to the above components, the thermoplastic elastomer composition of the present invention includes various anti-blocking agents, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, foaming depending on the application. It is also possible to contain a coloring agent, a coloring agent and the like. Here, as the antioxidant, for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 -Bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro-5, Phenolic antioxidants such as 5-undecane, phosphite antioxidants, thioether antioxidants, and the like can be used. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the components (A) to (D) contained in the thermoplastic elastomer composition of the present invention. More preferably, the content is 0.05 to 1.0 part by mass.
＜熱可塑性エラストマー組成物の製造方法＞
　本発明の熱可塑性エラストマー組成物の製造方法としては、通常の樹脂組成物の製造あるいはゴム組成物の製造に際して用いられる方法が採用でき、単軸押出機、二軸押出機、バンバリーミキサー、加熱ロール、各種ニーダー等の溶融混練機を用いて各成分を均一に混合することにより製造できる。加工機の設定温度は１５０℃～３００℃の中から任意に選ぶことができる。また、熱可塑性エラストマー組成物の硬度は、ＪＩＳ　Ｄタイプで２０～５０になるように調整されることが好ましい。 <Method for producing thermoplastic elastomer composition>
As a method for producing the thermoplastic elastomer composition of the present invention, a method used for producing a normal resin composition or a rubber composition can be employed. A single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll It can be produced by uniformly mixing the components using a melt kneader such as various kneaders. The set temperature of the processing machine can be arbitrarily selected from 150 ° C to 300 ° C. The hardness of the thermoplastic elastomer composition is preferably adjusted so as to be 20 to 50 in the JIS D type.
　本発明の熱可塑性エラストマー組成物は、各種成形法、例えば押出成形、射出成形、中空成形、圧縮成形、カレンダー成形などの公知の方法を用いて、シート状、フィルム状、チューブ状などの任意の形状の成形体に成形することができる。また、本発明の熱可塑性エラストマー組成物は、二色成形法、インサート成形法、共押出などにより、プラスチック、布帛等の他の材料と複合化してなる複合成形体とすることも可能である。 The thermoplastic elastomer composition of the present invention can be obtained by using various molding methods, for example, extrusion molding, injection molding, hollow molding, compression molding, calendar molding, or any other method such as sheet, film, and tube. It can be formed into a shaped molded body. Moreover, the thermoplastic elastomer composition of the present invention can also be made into a composite molded body formed by compounding with other materials such as plastics and fabrics by two-color molding method, insert molding method, co-extrusion and the like.
　本発明の熱可塑性エラストマー組成物は、各種工業製品や工業部品の原料として使用することができる。具体的には、インストルメントパネル、センターパネル、センターコンソールボックス、ドアトリム、ピラー、アシストグリップ、ハンドル、エアバックカバー等の自動車内装部品；モール等の自動車外装部品；リモコンスイッチ、ＯＡ機器の各種キートップ、テレビ、ステレオ、掃除機等の家電部品；水中眼鏡、水中カメラのカバー等の水中使用製品；各種カバー部品；密閉性、防水性、防音性、防振性等を目的とした各種パッキン付き工業部品；ラック＆ピニオンブーツ、サスペンションブーツ、等速ジョイントブーツ等の自動車機能部品；電線被覆等の電気、電子部品；スポーツシューズ、ファッションサンダル等の履物用途；ベルト、ホース、チューブ；スポーツ用品；ドア、窓枠材などの建築用資材；各種継手；バルブ部品等に使用することができる。 The thermoplastic elastomer composition of the present invention can be used as a raw material for various industrial products and industrial parts. Specifically, automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, and airbag covers; automotive exterior parts such as malls; remote control switches and various key tops for OA equipment Home appliance parts such as TVs, stereos, vacuum cleaners, etc .; underwater products such as underwater glasses and underwater camera covers; various cover parts; industry with various packing for sealing, waterproofing, soundproofing, vibration-proofing, etc. Parts; Automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc .; Electrical and electronic parts such as wire coverings; Footwear applications such as sports shoes and fashion sandals; Belts, hoses, tubes; Building materials such as window frame materials; various joints; used for valve parts, etc. It can be.
　以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下の実施例および比較例の物性評価は、以下に示す方法によって行った。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The physical properties of the following examples and comparative examples were evaluated by the methods shown below.
（１）硬度
　実施例及び比較例で得られた熱可塑性エラストマー組成物を２３０℃で射出成形することによって厚さ２ｍｍのシートを得た。このシートを用いて、ＪＩＳ Ｋ ６２５３に準拠してＪＩＳ－Ｄ硬度を測定した。
（２）ＭＦＲ
　実施例及び比較例で得られた熱可塑性エラストマー組成物を用いて、ＪＩＳ　Ｋ　７２１０に準拠して１９０℃、２１Ｎ荷重条件でのＭＦＲ（ｇ／１０分）を測定し、流動特性の指標とした。
（３）破断強度、破断伸度
　実施例及び比較例で得られた熱可塑性エラストマー組成物を２３０℃で射出成形することによって厚さ２ｍｍのシートを得た。このシートよりＪＩＳ Ｋ ６２５１に準拠したダンベル３号型の試験片を打ち抜いて作製し、引張試験を２３℃の温度条件および５００ｍｍ／分の引張速度条件下で実施して破断強度、破断伸度を測定した。
（４）引裂き強度
　実施例及び比較例で得られた熱可塑性エラストマー組成物を２３０℃で射出成形することによって厚さ２ｍｍのシートを得た。それから切込み無しのアングル形状試験片を打ち抜き、ＪＩＳ Ｋ ６２５２に準じて引裂き試験を行い、引裂き強度を測定した。
（５）耐熱性
　実施例および比較例で得られた熱可塑性エラストマー組成物の射出成形シートを１２０℃の条件下で１時間加熱し、収縮及び歪みを観察し、耐熱性の指標とした（収縮及び歪み無し：○、収縮及び歪み有り：×）。
（６）耐白化性
　実施例および比較例で得られた熱可塑性エラストマー組成物の射出成形シートを９０度折り曲げた後に元に戻し、白化の状態を観察し、耐白化性の指標とした（白化無し：○、僅かに白化有り：△、白化有り：×）。
（７）薄肉成形性
　実施例および比較例で得られた熱可塑性エラストマー組成物を２３０℃で、厚さ０．５ｍｍ×幅４０ｍｍの金型に射出成形を行い、ゲート近傍でのデラミ、フローマーク、ショートショット等の外観不良を観察し薄肉成形性の指標とした（◎：非常に良好、○：良好、△：僅かに不良発生、×：不良発生）。
（８）表面性
　実施例および比較例で得られた熱可塑性重合体組成物の射出成形シートを指先でなぞることにより、表面性の指標とした（べとつき無し：○、べとつき有り：×）。 (1) Hardness A sheet having a thickness of 2 mm was obtained by injection molding the thermoplastic elastomer compositions obtained in Examples and Comparative Examples at 230 ° C. Using this sheet, the JIS-D hardness was measured in accordance with JIS K 6253.
(2) MFR
Using the thermoplastic elastomer compositions obtained in Examples and Comparative Examples, MFR (g / 10 min) under a load condition of 190 ° C. and 21 N was measured according to JIS K 7210, and used as an index of flow characteristics. .
(3) Breaking strength and breaking elongation The thermoplastic elastomer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a thickness of 2 mm. A dumbbell No. 3 type test piece conforming to JIS K 6251 is punched out from this sheet, and a tensile test is performed under a temperature condition of 23 ° C. and a tensile speed condition of 500 mm / min to determine the breaking strength and breaking elongation. It was measured.
(4) Tear strength The thermoplastic elastomer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a thickness of 2 mm. Then, an angle-shaped test piece without incision was punched out, a tear test was performed according to JIS K 6252, and the tear strength was measured.
(5) Heat resistance The injection molded sheets of the thermoplastic elastomer compositions obtained in the examples and comparative examples were heated for 1 hour under the condition of 120 ° C., and the shrinkage and distortion were observed as a heat resistance index (shrinkage And no distortion: ○, shrinkage and distortion: x).
(6) Whitening resistance The injection molded sheets of the thermoplastic elastomer compositions obtained in the examples and comparative examples were folded 90 degrees and then returned to the original, and the whitening state was observed and used as an index of whitening resistance (whitening None: ○, slight whitening: Δ, whitening: x).
(7) Thin-wall moldability The thermoplastic elastomer compositions obtained in the examples and comparative examples were injection-molded into a mold having a thickness of 0.5 mm and a width of 40 mm at 230 ° C., and delamination and flow marks near the gate. The appearance defects such as short shots were observed and used as indicators of thin-wall moldability (◎: very good, ○: good, Δ: slightly defective, ×: defective).
(8) Surface property The injection-molded sheet of the thermoplastic polymer composition obtained in the examples and comparative examples was traced with a fingertip to obtain an index of surface property (no stickiness: ◯, with stickiness: x).
＜実施例１～４及び比較例１～８＞
　二軸押出機（口径４６ｍｍ、Ｌ／Ｄ＝４６）を使用して、下記の各構成成分を表１に示す配合に従って混合した後、２００℃で溶融混練し、ペレット状の熱可塑性エラストマー組成物を得た。これらの熱可塑性エラストマー組成物を用いて、射出成形機（２００℃）で、厚さ２ｍｍ×φ１２０ｍｍの円盤状の射出成形シートを作製した。 <Examples 1 to 4 and Comparative Examples 1 to 8>
Using a twin screw extruder (caliber 46 mm, L / D = 46), the following components were mixed according to the formulation shown in Table 1 and then melt-kneaded at 200 ° C. to form a pellet-shaped thermoplastic elastomer composition Got. Using these thermoplastic elastomer compositions, a disk-shaped injection-molded sheet having a thickness of 2 mm × φ120 mm was produced with an injection molding machine (200 ° C.).
＜水添ブロック共重合体（Ａ）＞
・成分（ａ－１）
セプトン４０５５（商品名）、株式会社クラレ製、水添スチレン系トリブロック共重合体、スチレン含有量：３０質量％、５質量％トルエン溶液において３０℃で測定された溶液粘度：９０ｍＰａ・ｓ（東京計器社製Ｂ形粘度計Ｂ８Ｌ、Ｎｏ．２ローター、回転数６０ｒｐｍにて測定）、水素添加率：９８％
・成分（ａ－２）
セプトン８００６（商品名）、株式会社クラレ製、水添スチレン系トリブロック共重合体、スチレン含有量：３３質量％、５質量％トルエン溶液において３０℃で測定された溶液粘度：４２ｍＰａ・ｓ（東京計器社製Ｂ形粘度計Ｂ８Ｌ、Ｎｏ．２ローター、回転数６０ｒｐｍにて測定）、水素添加率：９８％ <Hydrogenated block copolymer (A)>
・ Ingredient (a-1)
Septon 4055 (trade name), manufactured by Kuraray Co., Ltd., hydrogenated styrene-based triblock copolymer, styrene content: 30 mass%, solution viscosity measured at 30 ° C. in a 5 mass% toluene solution: 90 mPa · s (Tokyo) B type viscometer B8L manufactured by Keiki Co., Ltd., measured with a No. 2 rotor and a rotation speed of 60 rpm), hydrogenation rate: 98%
・ Ingredient (a-2)
Septon 8006 (trade name), manufactured by Kuraray Co., Ltd., hydrogenated styrene-based triblock copolymer, styrene content: 33 mass%, solution viscosity measured at 30 ° C. in a 5 mass% toluene solution: 42 mPa · s (Tokyo) B type viscometer B8L manufactured by Keiki Co., Ltd., measured with a No. 2 rotor and a rotation speed of 60 rpm), hydrogenation rate: 98%
＜炭化水素系ゴム用軟化剤（Ｂ）＞
・成分（ｂ－１）
ダイアナプロセスオイルＰＷ９０（商品名）、出光石油化学株式会社製、パラフィン系オイル、動粘度（４０℃）：９５．５ｍｍ２／ｓ、環分析パラフィン：７１％、環分析ナフテン：２９％
・成分（ｂ－２）
ＫｉｘｘＰＯ８（商品名）、ＧＳ　カルテックスコーポレーション製、パラフィン系オイル、動粘度（４０℃）：４９．４ｍｍ２／ｓ、環分析パラフィン：７９％、環分析ナフテン：２１％ <Softener for hydrocarbon rubber (B)>
・ Ingredient (b-1)
Diana Process Oil PW90 (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., paraffinic oil, kinematic viscosity (40 ° C.): 95.5 mm 2 / s, ring analysis paraffin: 71%, ring analysis naphthene: 29%
・ Ingredient (b-2)
KixxPO8 (trade name), manufactured by GS Caltex Corporation, paraffinic oil, kinematic viscosity (40 ° C.): 49.4 mm 2 / s, ring analysis paraffin: 79%, ring analysis naphthene: 21%
＜ポリオレフィン系重合体（Ｃ）＞
・成分（ｃ－１）
プライムポリプロピレン　Ｊ７０８ＵＧ（商品名）、プライムポリマー株式会社製、ブロックポリプロピレン、ＭＦＲ（２３０℃、２１．１８Ｎ）：４５ｇ／１０分、エチレン系重合体含有量：１４質量％
・成分（ｃ－２）
プライムポリプロピレン　Ｊ１０８Ｍ（商品名）、プライムポリマー株式会社製、ホモポリプロピレン、ＭＦＲ（２３０℃、２１．１８Ｎ）：４５ｇ／１０分、エチレン系重合体含有量：０質量％
・成分（ｃ－３）
ノバテックポリエチレン　ＬＪ８０４１（商品名）、日本ポリプロピレン株式会社製、低密度ポリエチレン（ＬＤＰＥ）、ＭＦＲ（１９０℃、２１．１８Ｎ）：２３ｇ／１０分、エチレン系重合体含有量：１００質量％。 <Polyolefin polymer (C)>
・ Ingredient (c-1)
Prime polypropylene J708UG (trade name), manufactured by Prime Polymer Co., Ltd., block polypropylene, MFR (230 ° C., 21.18 N): 45 g / 10 min, ethylene polymer content: 14% by mass
・ Ingredient (c-2)
Prime polypropylene J108M (trade name), manufactured by Prime Polymer Co., Ltd., homopolypropylene, MFR (230 ° C., 21.18N): 45 g / 10 min, ethylene polymer content: 0% by mass
・ Ingredient (c-3)
Novatec Polyethylene LJ8041 (trade name), manufactured by Nippon Polypropylene Co., Ltd., low density polyethylene (LDPE), MFR (190 ° C., 21.18 N): 23 g / 10 minutes, ethylene polymer content: 100% by mass.
＜シリコーンオイル（Ｄ）＞
・成分（ｄ－１）
ジメチルシリコーンオイル　ＡＫ３５（商品名）、旭化成ワッカーシリコーン株式会社製、動粘度（２５℃）：３５ｍｍ２／ｓ
・成分（ｄ－２）
ジメチルシリコーンオイル　ＡＫ３５０（商品名）、旭化成ワッカーシリコーン株式会社製、動粘度（２５℃）：３５０ｍｍ２／ｓ <Silicone oil (D)>
・ Ingredient (d-1)
Dimethyl silicone oil AK35 (trade name), Asahi Kasei Wacker Silicone Co., kinematic viscosity (25 ℃): 35mm 2 / s
・ Ingredient (d-2)
Dimethyl silicone oil AK350 (trade name), manufactured by Asahi Kasei Wacker Silicone Co., Ltd., kinematic viscosity (25 ° C.): 350 mm 2 / s
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記の結果から、本発明で規定する水添ブロック共重合体（Ａ）、炭化水素系ゴム用軟化剤（Ｂ）、オレフィン系樹脂（Ｃ）及びシリコーンオイル（Ｄ）を含有する実施例１～４の熱可塑性エラストマー組成物は、良好な耐熱性、流動性、耐白化性、表面性、力学物性、薄肉成形性を示すことが分かる。
　これに対し、比較例１及び２の熱可塑性エラストマー組成物は、オレフィン系樹脂（Ｃ）中のエチレン系重合体の含有量が２０質量％を越えるため、力学物性（引張強さ、切断時伸び）、流動性、耐白化性、薄肉成形性に劣る。
　比較例３の熱可塑性エラストマー組成物は、溶液粘度が５０ｍＰａ・ｓ未満で本発明の範囲外である水添ブロック共重合体を用いているため、力学物性（引張強度）及び耐白化性に劣る。
　比較例４及び５の熱可塑性エラストマー組成物は、溶液粘度が５０ｍＰａ・ｓ未満で本発明の範囲外である水添ブロック共重合体を用い、かつオレフィン系樹脂（Ｃ）中のエチレン系重合体の含有量が２０質量％を越えているため、力学物性（引張強さ、切断時伸び）、流動性、耐白化性、薄肉成形性に劣る。
　比較例６の熱可塑性エラストマー組成物は、オレフィン系樹脂（Ｃ）がエチレン系重合体を含まないために、耐白化性、薄肉成形性に劣る。
　比較例７の熱可塑性エラストマー組成物は、シリコーンオイル（Ｄ）の粘度が３５０ｍｍ２/ｓを越えているため、表面性に劣る。
　比較例８はポリエチレン単独であるため力学物性（引張強さ、切断時伸び）、耐熱性に劣る。 From the above results, Examples 1 to 4 containing the hydrogenated block copolymer (A), the hydrocarbon rubber softener (B), the olefin resin (C) and the silicone oil (D) specified in the present invention are used. It can be seen that the thermoplastic elastomer composition No. 4 exhibits good heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin moldability.
In contrast, in the thermoplastic elastomer compositions of Comparative Examples 1 and 2, the content of the ethylene polymer in the olefin resin (C) exceeds 20% by mass, so mechanical properties (tensile strength, elongation at break) ), Poor fluidity, whitening resistance, and thin-wall formability.
Since the thermoplastic elastomer composition of Comparative Example 3 uses a hydrogenated block copolymer having a solution viscosity of less than 50 mPa · s and outside the scope of the present invention, it is inferior in mechanical properties (tensile strength) and whitening resistance. .
The thermoplastic elastomer compositions of Comparative Examples 4 and 5 use a hydrogenated block copolymer having a solution viscosity of less than 50 mPa · s and outside the scope of the present invention, and an ethylene polymer in the olefin resin (C). Is more than 20% by mass, it is inferior in mechanical properties (tensile strength, elongation at break), fluidity, whitening resistance, and thin-wall moldability.
The thermoplastic elastomer composition of Comparative Example 6 is inferior in whitening resistance and thin-wall moldability because the olefin resin (C) does not contain an ethylene polymer.
The thermoplastic elastomer composition of Comparative Example 7 has poor surface properties because the viscosity of the silicone oil (D) exceeds 350 mm 2 / s.
Since Comparative Example 8 is polyethylene alone, it has poor mechanical properties (tensile strength, elongation at break) and heat resistance.
　本発明の熱可塑性エラストマー組成物は、耐熱性、流動性、耐白化性、表面性、力学物性及び薄肉成形性に優れているため、自動車内装材、外装材、床材、家電製品部品、食品用器具、オーディオ機器、ＯＡ機器等の部品、各種スイッチ、光ケーブル、スポーツ用品、靴、建材、玩具、文具等の幅広い用途に有効に使用することができる。 The thermoplastic elastomer composition of the present invention is excellent in heat resistance, fluidity, whitening resistance, surface properties, mechanical properties, and thin-wall moldability, so that it can be used for automobile interior materials, exterior materials, floor materials, home appliance parts, foods, etc. It can be used effectively in a wide range of applications such as parts for appliances, audio equipment, OA equipment, various switches, optical cables, sports equipment, shoes, building materials, toys, stationery, and the like.

Claims (4)

  1. 　芳香族ビニル化合物からなる重合体ブロック（ａ）と、共役ジエン化合物からなる重合体ブロック（ｂ）とを含有するブロック共重合体を水素添加して得られ、５質量％トルエン溶液において３０℃で測定した溶液粘度が５０～２００ｍＰａ・ｓの範囲にある水添ブロック共重合体（Ａ）１００質量部、炭化水素系ゴム用軟化剤（Ｂ）１５０～３５０質量部、プロピレン系重合体とエチレン系重合体を含み、エチレン系重合体の含有量が１～２０質量％であるオレフィン系樹脂（Ｃ）１５０～３５０質量部、及び２５℃で測定した動粘度が２００ｍｍ２/ｓ以下であるシリコーンオイル（Ｄ）０．０５～３質量部を含有する熱可塑性エラストマー組成物。 It is obtained by hydrogenating a block copolymer containing a polymer block (a) composed of an aromatic vinyl compound and a polymer block (b) composed of a conjugated diene compound at 30 ° C. in a 5% by mass toluene solution. 100 parts by mass of a hydrogenated block copolymer (A) having a measured solution viscosity in the range of 50 to 200 mPa · s, 150 to 350 parts by mass of a softening agent for hydrocarbon rubber (B), a propylene polymer and an ethylene system It includes a polymer, ethylene polymer of the olefin resin (C) 150 ~ 350 parts by weight content of 1 to 20 wt%, and silicone oil kinematic viscosity measured at 25 ° C. is not more than 200 mm 2 / s (D) A thermoplastic elastomer composition containing 0.05 to 3 parts by mass.
  2. 　前記共役ジエン化合物がイソプレン及びブタジエンから選ばれる少なくとも１種である請求項１に記載の熱可塑性エラストマー組成物。 The thermoplastic elastomer composition according to claim 1, wherein the conjugated diene compound is at least one selected from isoprene and butadiene.
  3. 　前記炭化水素系ゴム用軟化剤（Ｂ）の４０℃で測定した動粘度が１００ｍｍ２/ｓ以下である請求項１又は２に記載の熱可塑性エラストマー組成物。 The thermoplastic elastomer composition according to claim 1 or 2, wherein the hydrocarbon rubber softener (B) has a kinematic viscosity measured at 40 ° C of 100 mm 2 / s or less.
  4. 　前記炭化水素系ゴム用軟化剤（Ｂ）は、環分析によるパラフィン含有量が７３％以上である請求項１～３のいずれかに記載の熱可塑性エラストマー組成物。 The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the hydrocarbon rubber softener (B) has a paraffin content by ring analysis of 73% or more.
PCT/JP2014/077610 2013-10-25 2014-10-16 Thermoplastic elastomer composition WO2015060201A1 (en)

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JP2000256522A (en) * 1999-03-11 2000-09-19 Kinugawa Rubber Ind Co Ltd Tackless elastomer composition
JP2002173576A (en) * 2000-12-05 2002-06-21 Sumitomo Bakelite Co Ltd Thermoplastic elastomer composition
JP2002348435A (en) * 2001-05-24 2002-12-04 Japan Polyolefins Co Ltd Composite molding
JP2004075945A (en) * 2002-08-22 2004-03-11 Mitsuboshi Belting Ltd Thermoplastic elastomer composition for slush molding, powder, and skin material therewith
JP2008264242A (en) * 2007-04-20 2008-11-06 Aron Kasei Co Ltd Thermoplastic elastomer composition and cover for mouth part stopper body of liquid medicine container using the same
WO2011155571A1 (en) * 2010-06-09 2011-12-15 旭化成ケミカルズ株式会社 Thermoplastic elastomer composition and molded articles thereof
JP2013053319A (en) * 2008-10-08 2013-03-21 Aron Kasei Co Ltd Elastomer composition for extrusion molding and film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000256522A (en) * 1999-03-11 2000-09-19 Kinugawa Rubber Ind Co Ltd Tackless elastomer composition
JP2002173576A (en) * 2000-12-05 2002-06-21 Sumitomo Bakelite Co Ltd Thermoplastic elastomer composition
JP2002348435A (en) * 2001-05-24 2002-12-04 Japan Polyolefins Co Ltd Composite molding
JP2004075945A (en) * 2002-08-22 2004-03-11 Mitsuboshi Belting Ltd Thermoplastic elastomer composition for slush molding, powder, and skin material therewith
JP2008264242A (en) * 2007-04-20 2008-11-06 Aron Kasei Co Ltd Thermoplastic elastomer composition and cover for mouth part stopper body of liquid medicine container using the same
JP2013053319A (en) * 2008-10-08 2013-03-21 Aron Kasei Co Ltd Elastomer composition for extrusion molding and film
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