WO2021024347A1 - Thermoplastic elastomer composition - Google Patents

Thermoplastic elastomer composition Download PDF

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Publication number
WO2021024347A1
WO2021024347A1 PCT/JP2019/030681 JP2019030681W WO2021024347A1 WO 2021024347 A1 WO2021024347 A1 WO 2021024347A1 JP 2019030681 W JP2019030681 W JP 2019030681W WO 2021024347 A1 WO2021024347 A1 WO 2021024347A1
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Prior art keywords
mass
molecular weight
elastomer composition
thermoplastic elastomer
styrene
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PCT/JP2019/030681
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French (fr)
Japanese (ja)
Inventor
憲昭 伊達
悠 松本
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アロン化成株式会社
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Priority to JP2021538562A priority Critical patent/JP7157257B2/en
Priority to PCT/JP2019/030681 priority patent/WO2021024347A1/en
Publication of WO2021024347A1 publication Critical patent/WO2021024347A1/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
    • 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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene

Definitions

  • the present invention relates to a thermoplastic elastomer composition used for various molded products such as automobiles, electronic materials, home appliances, electric devices, medical tools, packaging materials, stationery and miscellaneous goods.
  • thermoplastic elastomer which is a soft material and does not require a vulcanization process and has molding processability similar to that of a thermoplastic resin.
  • various polymers such as polyolefin-based, polyurethane-based, polyester-based, and polystyrene-based polymers have been developed and are commercially available for such thermoplastic elastomers.
  • thermoplastic styrene-based elastomers are widely used in terms of workability and cost, but in the case of low hardness type, molding defects such as flow marks occur during injection molding. However, it often spoils the appearance.
  • Patent Document 1 discloses that the generation of flow marks can be prevented by using a propylene / ethylene copolymer as a moldability modifier for a polypropylene-based resin, and as a principle thereof, low viscosity. It has been suggested that the flow of the molten resin is stabilized by adding a small amount of a propylene / ethylene random copolymer having a difference in viscosity to a propylene homopolymer having a high MFR.
  • Patent Document 2 discloses that a propylene-based resin composition composed of a propylene / ethylene block copolymer having a diewell ratio of 1.7 or more, an ethylene-based elastomer, and a filler is less likely to cause flow marks, and is optional. It is suggested that it is preferable to blend a styrene-based elastomer having an MFR of 5 g / 10 minutes or more at 230 ° C. and 21.2 N as a component.
  • the propylene-based resin composition is effective in improving the flow mark, but the effect is not clear in the resin composition in which the styrene-based elastomer such as SEBS is present.
  • Patent Document 2 suggests that it is not preferable to blend a styrene-based elastomer, which is an optional component, with an MFR of less than 5 g / 10 minutes at 230 ° C. and 21.2 N because the flow mark property is lowered.
  • MFR MFR of less than 5 g / 10 minutes at 230 ° C. and 21.2 N because the flow mark property is lowered.
  • the grades that can be used with styrene-based elastomers, which are generally considered to have low fluidity, are limited.
  • An object of the present invention is to provide a thermoplastic elastomer composition which is excellent in moldability and mechanical strength and can minimize the occurrence of flow marks.
  • the present invention [1] Containing a thermoplastic styrene-based elastomer A, a propylene homopolymer B, and a softening agent C, the content of the propylene homopolymer B is 10 to 400 mass by mass with respect to 100 parts by mass of the thermoplastic styrene-based elastomer A.
  • the content of the softener C is 10 to 300 parts by mass, the ratio of the weight average molecular weight to the number average molecular weight of the propylene homopolymer B (weight average molecular weight / number average molecular weight) is 10.0 to 25.0, and the swell ratio.
  • Thermoplastic elastomer composition which is 1.1-2.5.
  • thermoplastic elastomer composition according to [1] above, wherein the melt mass flow rate of the propylene homopolymer B at 230 ° C. and a nominal load of 21.2 N is 1 to 30 g / 10 min.
  • propylene homopolymer D having a melt mass flow rate of 100 g / 10 min or more at 230 ° C. and a nominal load of 21.2 N is contained in an amount of 3 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic styrene elastomer A.
  • thermoplastic elastomer composition according to [2] above, wherein the content of the propylene homopolymer D is 1 to 80 parts by mass with respect to 100 parts by mass of the propylene homopolymer B.
  • thermoplastic elastomer composition according to any one of [1] to [5] above, wherein the thermoplastic styrene elastomer A contains a controlled distribution type styrene block copolymer.
  • thermoplastic elastomer composition according to any one of [1] to [6] above, wherein the softener C contains at least one selected from paraffinic oils and naphthenic oils.
  • thermoplastic elastomer composition of the present invention has excellent moldability and mechanical strength, and has the effect of minimizing the occurrence of flow marks.
  • the thermoplastic elastomer composition of the present invention contains a thermoplastic styrene elastomer A, a propylene homopolymer B, and a softening agent C, and is molded by a propylene homopolymer B having a specific molecular weight distribution and swell ratio. It has one feature in that the occurrence of flow marks at the time is improved, and although the details are unknown, it is presumed as follows. In order to improve the occurrence of flow marks, it is necessary to stabilize the movement of the flow end during resin flow. When the swell ratio of the resin is increased, the force of the resin to spread (first normal stress) improves the transfer to the mold surface and reduces the flow mark.
  • thermoplastic styrene-based elastomer A in the present invention is preferably composed of a hard portion (hard segment) and a soft portion (soft segment), and the styrene-based single amount as the hard segment. More preferably, it is a block copolymer (Z1) having a block unit (s1) of a polymer composed of a body and a block unit (b1) of a polymer composed of a conjugated diene compound as a soft segment.
  • styrene-based monomer constituting the block unit (s1) examples include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, and the like.
  • examples include vinyl anthracene.
  • the content of the block unit (s1) in the block copolymer (Z1) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
  • Examples of the conjugated diene compound constituting the block unit (b1) include butadiene, isoprene, 1,3-pentadiene and the like.
  • the block copolymer (Z1) is preferably hydrogenated in part or in whole because unsaturated bonds are reduced by hydrogenation and heat resistance, weather resistance and mechanical properties are improved. ..
  • the hydrogenation rate is preferably 80% or more, more preferably 90% or more.
  • the hydrogenation rate is determined by measuring the content of carbon-carbon double bonds derived from the conjugated diene compound in the block copolymer before and after hydrogenation by 1H-NMR spectrum, and from the measured values. Can be sought.
  • hydrogenated product of the block copolymer (Z1) include styrene-ethylene / butylene block copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene / propylene block copolymer.
  • SEBS styrene-ethylene / butylene block copolymer
  • SEBS styrene-ethylene / propylene block copolymer
  • styrene-ethylene / propylene-styrene block copolymer SEPS
  • styrene-ethylene-ethylene / propylene block copolymer SEPS
  • styrene- (ethylene-ethylene / propylene) -styrene block copolymer SEEPS
  • SEEPS styrene- Isobutylene block copolymer
  • styrene-isobutylene-styrene block copolymer ( ⁇ -methylstyrene) -ethylene-butylene block copolymer
  • block Examples include polymers. These may be used alone or as a mixture of two or more kinds, but SEBS, SEPS, and SEEPS are preferable, and SEBS is more preferable, from the viewpoint of raw material preparation and workability.
  • the thermoplastic styrene-based elastomer A is more [block unit (s1) -block unit (b1)] than the [block unit (s1) -block unit (b1)] type diblock copolymer from the viewpoint of heat resistance.
  • b1) -block unit (s1)] type triblock copolymers are preferred.
  • the triblock copolymers include SEBS, SEPS, SEEPS, SEB (S) S, styrene-isobutylene-styrene block copolymer, ( ⁇ -methylstyrene) -ethylene-butylene- ( Examples thereof include ⁇ -methylstyrene) block copolymers.
  • the content of the triblock copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more in the styrene-based block copolymer A.
  • thermoplastic styrene-based elastomer A is preferably not acid-modified from the viewpoint that those having various properties are industrially mass-produced and easily available.
  • the thermoplastic styrene-based elastomer A may be a controlled distribution type styrene-based block copolymer.
  • the controlled distribution type styrene block copolymer is a copolymer unit of a conjugated diene and a styrene monomer instead of the block unit (b1), and has a block unit (b1') having a controlled distribution structure. Is preferable.
  • the block unit (b1') has two or more regions containing a conjugated diene unit as a main constituent unit and one or more regions containing a styrene-based monomer unit as a main constituent unit, and is a block unit (s1). Both ends adjacent to are preferably regions containing a conjugated diene unit as a main constituent unit.
  • the content of the styrene-based monomer unit in the controlled distribution type styrene-based block copolymer A is preferably 45 to 80% by mass, more preferably 50 to 75% by mass, from the viewpoint of heat-sealing property with the polar resin. , More preferably 55-70% by mass.
  • the content of the styrene-based monomer unit in the controlled distribution type styrene-based block copolymer A is the total amount of the styrene-based monomer unit in the hard segment and the styrene-based monomer unit in the soft segment.
  • controlled distribution type styrene-based elastomer block copolymer is well known in the art, and is described in, for example, Japanese Patent Application Laid-Open No. 2007-84421 and Japanese Patent Application Laid-Open No. 2013-518170.
  • the weight average molecular weight of the thermoplastic styrene-based elastomer A is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 200,000 or more, and easy to flow during heating, from the viewpoints of oil bleed resistance, heat resistance and mechanical properties. That is, from the viewpoint of moldability at the time of manufacture, it is preferably 500,000 or less, more preferably 400,000 or less, and further preferably 300,000 or less.
  • the thermoplastic styrene-based elastomer A is composed of a plurality of elastomers, it is preferable that the weighted average value of the weight average molecular weight of each elastomer falls within the above range.
  • the content of the thermoplastic styrene-based elastomer A in the thermoplastic elastomer composition is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
  • thermoplastic styrene-based elastomer A may be composed of one type or two or more types may be used in combination, and the same applies to the propylene homopolymer B and the softening agent C described later. ..
  • the propylene homopolymer B in the present invention is generally called a homopolypropylene resin.
  • Other propylene-based polymers other than the homopolypropylene resin include block polypropylene, random polypropylene, and the like. These may be contained in the thermoplastic elastomer composition as long as the effect of the present invention is not impaired.
  • the propylene homopolymer B two or more kinds of propylene homopolymers may be used in combination.
  • Polypropylene homopolymer B can be obtained by an existing slurry process (polymerization in a liquid monomer), gas phase polymerization, or the like. Further, each subsequent polymerization may be obtained by a step-growth polymerization method comprising at least two step-growth polymerization stages in which the subsequent polymerization is carried out in the presence of a polymerizable substance formed during the immediately preceding polymerization reaction.
  • the polymerization is preferably carried out in the presence of a stereospecific Ziegler-Natta catalyst.
  • a solid catalyst containing A) an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component;
  • B an organoaluminum compound; and, if necessary, (C). Examples thereof include methods performed in the presence of a catalytic component containing an external electron donor compound selected from silicon compounds.
  • the stereospecific Ziegler-Natta catalyst is a catalyst well known in patent documents and the like.
  • the swell ratio of the propylene homopolymer B is 1.1 to 2.5, preferably 1.2 to 2.0. If the swell ratio is less than 1.1, flow marks tend to occur, and if it exceeds 2.5, it tends to be difficult to manufacture at low cost in a general-purpose manufacturing process.
  • the propylene homopolymer B is composed of two or more kinds of propylene homopolymers, it is preferable that the swell ratio of each propylene homopolymer is within the above range. The same applies to the physical characteristics such as the average molecular weight described later.
  • the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) of the propylene homopolymer B is 10.0 to 25.0, preferably 11.0 to 24.0. If the molecular weight distribution is less than 10.0, the effect of improving the flow mark is inferior, while if it exceeds 25.0, production becomes difficult.
  • the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is an index of the molecular weight distribution, and the larger the ratio, the wider the molecular weight distribution.
  • the weight average molecular weight of the propylene homopolymer B is preferably 350,000 or more, more preferably 400,000 or more, and preferably 550,000 or less, more preferably 500,000 or less, from the viewpoint of mechanical properties.
  • the z average molecular weight is preferably 1,000,000 or more, more preferably 1,500,000 or more, and preferably 3,000,000 or less, more preferably 2,000,000 or less.
  • the propylene homopolymer B preferably has high fluidity from the viewpoint of dispersibility and moldability of the thermoplastic elastomer composition.
  • the fluidity can be evaluated by melt mass flow rate (MFR) and is 230 ° C., nominal load 21.2 N, preferably 0.1 g / 10 min or higher, more preferably 1 g / 10 min or higher, in the process of manufacturing the composition. From the viewpoint of ease of kneading, it is preferably 50 g / 10 min or less, more preferably 40 g / 10 min or less, further preferably 30 g / 10 min or less, still more preferably 15 g / 10 min or less.
  • the content of the propylene homopolymer B is 10 parts by mass or more, preferably 30 parts by mass or more from the viewpoint of moldability with respect to 100 parts by mass of the thermoplastic styrene elastomer A, and 400 by mass from the viewpoint of flexibility. It is by mass or less, preferably 300 parts by mass or less, and more preferably 100 parts by mass or less.
  • the content of the propylene homopolymer B in the thermoplastic elastomer composition is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 20 parts by mass.
  • softening agent C examples include softening agents for rubber such as paraffin-based oils, naphthen-based oils, and aromatic oils.
  • softeners C have good affinity with thermoplastic styrene-based elastomers and bleed. From the viewpoint of being less likely to occur, at least one selected from paraffin-based oil and naphthen-based oil is preferable, and paraffin-based oil is more preferable.
  • the content of the softener C is 10 parts by mass or more, preferably 50 parts by mass or more from the viewpoint of flexibility, and 300 parts by mass from the viewpoint of suppressing oil bleeding, with respect to 100 parts by mass of the thermoplastic styrene elastomer A. Parts or less, preferably 150 parts by mass or less.
  • the content of the softening agent C in the thermoplastic elastomer composition is preferably 5 to 65% by mass, more preferably 20 to 50% by mass.
  • thermoplastic elastomer composition of the present invention has a higher fluidity than the propylene homopolymer B, that is, a propylene homopolymer D having a large melt mass flow rate, from the viewpoint of increasing the fluidity of the composition and improving the moldability. It is preferable to further contain.
  • the melt mass flow rate (MFR) of the propylene homopolymer D at 230 ° C. and a nominal load of 21.2 N is preferably 100 g / 10 min or more, more preferably 500 g / 10 min or more, still more preferably 1000 g / 10 min or more, and also. It is preferably 5000 g / 10 min or less, and more preferably 3000 g / 10 min or less.
  • the swell ratio of the propylene homopolymer D is preferably 0.4 to 1.0, more preferably 0.6 to 0.8.
  • the ratio of the weight average molecular weight to the number average molecular weight of the propylene homopolymer D is preferably 1 to 15, more preferably 5 to 10.
  • the weight average molecular weight of the propylene homopolymer D is preferably 7,000 or more, more preferably 10,000 or more, and preferably 150,000 or less, more preferably 120,000 or less.
  • the z average molecular weight of the propylene homopolymer D is preferably 30,000 or more, more preferably 100,000 or more, and preferably 350,000 or less, more preferably 300,000 or less.
  • the content of the propylene homopolymer D is preferably equal to or less than the content of the propylene homopolymer B, and the content of the propylene homopolymer D with respect to 100 parts by mass of the propylene homopolymer B. Is preferably 1 to 100 parts by mass, more preferably 1 to 80 parts by mass, still more preferably 20 to 50 parts by mass.
  • the content of the propylene homopolymer D is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of the thermoplastic styrene elastomer A from the viewpoint of moldability. It is 400 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less.
  • the content of the propylene homopolymer D in the thermoplastic elastomer composition is preferably 1 to 40% by mass in the thermoplastic elastomer composition of the present invention.
  • the thermoplastic elastomer composition of the present invention may further contain a stabilizer.
  • a stabilizer Various stabilizers of the resin composition are known, but in the present invention, an antioxidant is used from the viewpoint of improving heat aging resistance, and an ultraviolet absorber and a light stabilizer are used from the viewpoint of improving weather resistance. However, each is preferable.
  • thermoplastic elastomer composition of the present invention may contain other thermoplastic resins or thermoplastic elastomers as long as the effects of the present invention are not impaired.
  • thermoplastic elastomer composition of the present invention is a reinforcing agent for carbon black, silica, carbon fiber, glass fiber, etc., as long as the effect of the present invention is not impaired; calcium carbonate, talc, clay, titanium oxide, mica, etc. It contains various additives such as fillers, insulating heat conductive fillers, talc, pigments, flame retardants, antistatic agents, mold release agents, tackifiers, cross-linking agents, cross-linking aids, foaming agents, and fragrances. May be good.
  • thermoplastic elastomer composition of the present invention a thermoplastic styrene elastomer A, a propylene homopolymer B, and a softening agent C, and if necessary, additives such as a propylene homopolymer D and an antioxidant are appropriately added. It is obtained by mixing and solidifying by cooling.
  • mixing is not particularly limited as long as it is a method in which various raw materials are mixed well, and various raw materials may be dissolved in a soluble organic solvent and mixed, or by melt kneading. Although they may be mixed, it is preferable to mix the raw materials under the condition that the raw materials are melted.
  • a general extruder In the case of melt-kneading, a general extruder can be used, and it is preferable to use a twin-screw extruder in order to improve the kneading state.
  • a mixing device such as a Henschel mixer in advance may be supplied from one hopper, or each component is charged into two hoppers and quantified with a screw or the like under the hopper. You may serve while.
  • the product obtained by mixing the raw materials constituting the thermoplastic elastomer composition can be in the form of pellets, powders, sheets, etc., depending on the application. For example, it is melt-kneaded by an extruder and extruded into a strand, and while being cooled in cold water, it is cut into pellets such as columns and rice granules by a cutter.
  • the obtained pellets are usually made into a predetermined sheet-shaped molded product or mold-molded product by injection molding or extrusion molding. Further, the melt-kneaded product can be pelletized with a ruder or the like and used as a raw material for molding. It may be an intermediate product in which a mount or the like is attached to a sheet-shaped thermoplastic elastomer composition.
  • the hardness of the thermoplastic elastomer composition of the present invention is A hardness, preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, and when the A hardness exceeds 90,
  • the upper limit of the hardness of the thermoplastic elastomer composition is D hardness, preferably 60 or less, more preferably 40 or less, and A hardness, preferably 90 or less, more preferably 80 or less. ..
  • the melt mass flow rate of the thermoplastic elastomer composition of the present invention at 200 ° C. and a nominal load of 49 N is preferably 6 to 30 g / 10 min, more preferably 10 to 20 g / 10 min, from the viewpoint of fluidity and moldability.
  • the swell ratio of the thermoplastic elastomer composition of the present invention is preferably 1.1 to 2.5, more preferably 1.2 to 2.0.
  • a molded product can be obtained by appropriately heat-molding the thermoplastic elastomer composition of the present invention according to a conventional method.
  • Any molding machine capable of melting the molding material can be used as the apparatus used for manufacturing the molded body, for example, a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, a mixing roll and the like. Can be mentioned.
  • thermoplastic elastomer composition of the present invention is not particularly limited, and general styrene-based elastomer, polyolefin-based elastomer, polyurethane-based elastomer, polyamide-based elastomer, and acrylic-based elastomer. It can be used in fields where or polyester elastomers are used.
  • the content of styrene and / or styrene derivative is determined by performing proton NMR measurement with a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400) and quantifying the characteristic group of styrene.
  • the content of other monomer units can also be determined by proton NMR measurement.
  • Weight average molecular weight (Mw) Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by a gel permeation chromatograph to determine the weight average molecular weight.
  • Measuring device / pump JASCO (JASCO Corporation), PU-980 ⁇ Column oven: Showa Denko KK, AO-50 ⁇ Detector: Hitachi, RI (differential refractometer) detector L-3300 -Column type: Showa Denko Corporation "K-805L (8.0 x 300 mm)" and "K-804L (8.0 x 300 mm)" are used in series.
  • Eluent Chloroform ⁇ Eluent flow rate: 1.0 ml / min ⁇ Sample concentration: Approximately 1 mg / ml ⁇
  • Sample solution filtration Polytetrafluoroethylene 0.45 ⁇ m pore size disposable filter ⁇ Standard sample for calibration curve: Polystyrene manufactured by Showa Denko KK
  • ⁇ Component B and Component D Propylene homopolymer, etc.> [Swell ratio] Using a capillary rheometer (Toyo Seiki Seisakusho Co., Ltd., Capillograph Graph 1D), measure the strand diameter of an extruded sample at 200 ° C., shear rate 100 (1 / sec), and orifice diameter 2.0 mm with a caliper, and perform strands. The swell ratio is the value obtained by dividing the diameter by the orifice diameter.
  • MFR Melt Mass Flow Rate
  • the molecular weight is measured in terms of polystyrene by a gel permeation chromatograph, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the z average molecular weight (Mz) are obtained, and the molecular weight distribution (Mw / Mn) is calculated.
  • GPC device GPCV2000 system (Waters Allince) ⁇ Guard column: GPC UT-G (Shodex) -Analytical column: GPC UT-807 + GPC UT-806M x 2 (Shodex) ⁇ Column temperature: 140 °C ⁇
  • Eluent Orthodichlorobenzene for high performance liquid chromatography containing 0.1w / v% BHT ⁇ Eluent flow rate: 1.0mL / min ⁇ Sample concentration: Approximately 0.8 mg / mL ⁇ Sample solution filtration: PTFE 0.5 ⁇ m pore size membrane filter ⁇ Injection volume: 317 ⁇ L -Standard sample: Standard polystyrene (Shodex STANDARD) Molecular weight: 7.30 ⁇ 10 6 , 3.85 ⁇ 10 6 , 2.06 ⁇ 10 6 , 6.66 ⁇ 10 5 , 1.33 ⁇ 10 5 , 5.51 ⁇ 10 4 , 2.86 ⁇ 10 4 , 7.
  • Examples 1 to 11 and Comparative Examples 1 to 9 (1) Preparation of Thermoplastic Elastomer Composition (Pellet)
  • the materials shown in Tables 6 to 8 other than the softener were dry-blended and then impregnated with the softener to prepare a mixture. Then, the mixture is melt-kneaded with an extruder under the following conditions, extruded into strands, and cut into a diameter of about 3 mm and a thickness of about 3 mm with a cutter while being cooled in cold water to obtain pellets of the thermoplastic elastomer composition. Manufactured.
  • Injection molding machine Injection molding machine: EC100SX II-4B (manufactured by Toshiba Machine Co., Ltd.) Injection molding temperature: 200 ° C Injection pressure: 120MPa Holding pressure 30MPa Injection time: 2sec Mold temperature: 40 °C
  • thermoplastic elastomer compositions obtained in Examples and Comparative Examples were evaluated as follows using the pellets or plates. The results are shown in Tables 6-8.
  • a hardness A hardness (value 1 second after the start of the test) was measured for a measurement time of 1 second in accordance with JIS K 6253 for a stack of 3 A hardness plates (total 6 mm). The measurement was carried out after adjusting the condition for one day in a room with a temperature of 23 ° C and a humidity of 50%.
  • the D-hardness (value 1 second after the start of the test) was measured for a measurement time of 1 second in accordance with JIS K 6253 for a stack of 3 plates (6 mm in total). The measurement was carried out after adjusting the condition for one day in a room with a temperature of 23 ° C and a humidity of 50%.
  • MFR Melt mass flow rate
  • Injection molding conditions Injection molding machine: EC100SX II-4B (manufactured by Toshiba Machine Co., Ltd.) Injection molding temperature: 200 ° C Injection pressure: 120MPa Holding pressure 30MPa Injection time: 2sec Mold temperature: 40 °C
  • thermoplastic elastomer compositions of Examples 1 to 11 can minimize the occurrence of flow marks as compared with Comparative Examples 2, 3 and 5 to 9, and are molded materials by injection molding. It turns out that it is also useful.
  • the flow mark can be improved more effectively by blending the propylene homopolymer D having a large MFR in an amount smaller than that of the propylene homopolymer B. I understand.
  • Comparative Example 1 although there is no problem with the flow mark, the MFR is too small, so that the moldability is good.
  • Comparative Example 4 although the flow mark is also not a problem, the hardness is too high and the flexibility is lacking. It can be seen that problems occur as molded products.
  • thermoplastic elastomer composition of the present invention can be used for various molded products such as automobiles, electronic materials, home appliances, electric devices, medical tools, packaging materials, stationery and miscellaneous goods, and further, tubes, cushions, films, etc. , Used for various members such as sheets.

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Abstract

This thermoplastic elastomer composition contains a thermoplastic styrene-based elastomer A, a propylene homopolymer B, and a softener C, wherein: the contained amount of the propylene homopolymer B is 10-400 parts by mass, and the contained amount of the softener C is 10-300 parts by mass, with respect to 100 parts by mass of the thermoplastic styrene-based elastomer A; and, regarding the propylene homopolymer B, the ratio (weight average molecular weight/number average molecular weight) between the weight average molecular weight and the number average molecular weight is 10.0-25.0, and the swelling ratio is 1.1-2.5. The thermoplastic elastomer composition according to the present invention can be used for various molded products such as automobiles, electronic materials, household electric appliances, electric devices, medical instruments, packaging materials, and stationery/miscellaneous goods, and can be also used for various members such as tubes, cushion bodies, films, and sheets.

Description

熱可塑性エラストマー組成物Thermoplastic elastomer composition
　本発明は、自動車、電子材料、家電、電気機器、医療用具、包装資材、文具・雑貨用品等の各種成形品等に使用される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 used for various molded products such as automobiles, electronic materials, home appliances, electric devices, medical tools, packaging materials, stationery and miscellaneous goods.
　従来から、軟質材料であって、加硫工程を要せず、熱可塑性樹脂と同様な成形加工性を有する熱可塑性エラストマーが存在する。このような熱可塑性エラストマーには現在、ポリオレフィン系、ポリウレタン系、ポリエステル系、ポリスチレン系等の種々のポリマーが開発され、市販されている。これらの熱可塑性エラストマーのなかでも、熱可塑性スチレン系エラストマーは加工性、コスト面より広く利用されているが、特に、低硬度タイプの場合は、射出成形の際、フローマーク等の成形不良が発生し、外観を損なう場合が多い。 Conventionally, there is a thermoplastic elastomer which is a soft material and does not require a vulcanization process and has molding processability similar to that of a thermoplastic resin. Currently, various polymers such as polyolefin-based, polyurethane-based, polyester-based, and polystyrene-based polymers have been developed and are commercially available for such thermoplastic elastomers. Among these thermoplastic elastomers, thermoplastic styrene-based elastomers are widely used in terms of workability and cost, but in the case of low hardness type, molding defects such as flow marks occur during injection molding. However, it often spoils the appearance.
　特許文献１には、ポリプロピレン系樹脂の成形性改質剤として、プロピレン・エチレン共重合体を用いることにより、フローマークの発生を防ぐことができることが開示されており、その原理として、低粘度・高ＭＦＲのプロピレン単独重合体に、粘度差に格差のあるプロピレン・エチレンランダム共重合体を少量添加することにより、溶融樹脂の流動が安定化されることが示唆されている。 Patent Document 1 discloses that the generation of flow marks can be prevented by using a propylene / ethylene copolymer as a moldability modifier for a polypropylene-based resin, and as a principle thereof, low viscosity. It has been suggested that the flow of the molten resin is stabilized by adding a small amount of a propylene / ethylene random copolymer having a difference in viscosity to a propylene homopolymer having a high MFR.
　特許文献２には、ダイスウェル比が1.7以上のプロピレン・エチレンブロック共重合体と、エチレン系エラストマー、及びフィラーからなるプロピレン系樹脂組成物はフローマークが発生し難いことが開示されており、任意成分として、230℃、21.2ＮにおけるＭＦＲが5g／10分以上のスチレン系エラストマーを配合することが好ましいことが示唆されている。 Patent Document 2 discloses that a propylene-based resin composition composed of a propylene / ethylene block copolymer having a diewell ratio of 1.7 or more, an ethylene-based elastomer, and a filler is less likely to cause flow marks, and is optional. It is suggested that it is preferable to blend a styrene-based elastomer having an MFR of 5 g / 10 minutes or more at 230 ° C. and 21.2 N as a component.
特開２００９-７３９４号公報JP-A-2009-7394 特開平６－２４８１５５号公報Japanese Unexamined Patent Publication No. 6-248155
　しかしながら、特許文献１ではプロピレン系樹脂組成物についてはフローマーク改善に効果が見られるが、ＳＥＢＳをはじめとしたスチレン系エラストマーが存在する樹脂組成物では効果が定かではない。 However, in Patent Document 1, the propylene-based resin composition is effective in improving the flow mark, but the effect is not clear in the resin composition in which the styrene-based elastomer such as SEBS is present.
　また、特許文献２では任意成分であるスチレン系エラストマーについて、230℃、21.2ＮにおけるＭＦＲが5g／10分未満のものを配合すると、フローマーク性が低下するので好ましくないことが示唆されており、一般的に流動性が低いとされているスチレン系エラストマーでは使用できるグレードが限定されてしまう。 Further, Patent Document 2 suggests that it is not preferable to blend a styrene-based elastomer, which is an optional component, with an MFR of less than 5 g / 10 minutes at 230 ° C. and 21.2 N because the flow mark property is lowered. The grades that can be used with styrene-based elastomers, which are generally considered to have low fluidity, are limited.
　本発明の課題は、成形性及び機械的強度に優れ、フローマークの発生を最小限にすることが可能である熱可塑性エラストマー組成物を提供することにある。 An object of the present invention is to provide a thermoplastic elastomer composition which is excellent in moldability and mechanical strength and can minimize the occurrence of flow marks.
　本発明は、
〔１〕　熱可塑性スチレン系エラストマーＡとプロピレン単独重合体Ｂと軟化剤Ｃを含有し、熱可塑性スチレン系エラストマーＡ 100質量部に対して、前記プロピレン単独重合体Ｂの含有量が10～400質量部、前記軟化剤Ｃの含有量が10～300質量部であり、前記プロピレン単独重合体Ｂの重量平均分子量と数平均分子量の比（重量平均分子量／数平均分子量）が10.0～25.0、スウェル比が1.1～2.5である、熱可塑性エラストマー組成物、
〔２〕　プロピレン単独重合体Ｂの230℃、公称荷重21.2Ｎでのメルトマスフローレイトが、1～30g/10minである、前記〔１〕記載の熱可塑性エラストマー組成物、
〔３〕　さらに、230℃、公称荷重21.2Ｎでのメルトマスフローレイトが100g/10min以上であるプロピレン単独重合体Ｄを、熱可塑性スチレン系エラストマーＡ100質量部に対して、3～400質量部含有し、該プロピレン単独重合体Ｄの含有量が、プロピレン単独重合体Ｂ 100質量部に対して、1～80質量部である、前記〔２〕載の熱可塑性エラストマー組成物、
〔４〕　プロピレン単独重合体Ｂのｚ平均分子量が、1,000,000～3,000,000である、前記〔３〕記載の熱可塑性エラストマー組成物、
〔５〕　熱可塑性スチレン系エラストマーＡの重量平均分子量が、50,000～500,000である、前記〔１〕～〔４〕いずれか記載の熱可塑性エラストマー組成物、
〔６〕　熱可塑性スチレン系エラストマーＡが、制御分布型スチレン系ブロック共重合体を含有する、前記〔１〕～〔５〕いずれか記載の熱可塑性エラストマー組成物、
〔７〕　軟化剤Ｃが、パラフィン系オイル及びナフテン系オイルから選択される少なくとも1種を含有する、前記〔１〕～〔６〕いずれか記載の熱可塑性エラストマー組成物、
〔８〕　熱可塑性エラストマー組成物のスウェル比が1.1～2.5である、前記〔１〕～〔７〕いずれか記載の熱可塑性エラストマー組成物、並びに
〔９〕　熱可塑性エラストマー組成物の200℃、公称荷重49Ｎでのメルトマスフローレイトが、6～30g/10minである、前記〔１〕～〔８〕いずれか記載の熱可塑性エラストマー組成物
に関する。 The present invention
[1] Containing a thermoplastic styrene-based elastomer A, a propylene homopolymer B, and a softening agent C, the content of the propylene homopolymer B is 10 to 400 mass by mass with respect to 100 parts by mass of the thermoplastic styrene-based elastomer A. The content of the softener C is 10 to 300 parts by mass, the ratio of the weight average molecular weight to the number average molecular weight of the propylene homopolymer B (weight average molecular weight / number average molecular weight) is 10.0 to 25.0, and the swell ratio. Thermoplastic elastomer composition, which is 1.1-2.5.
[2] The thermoplastic elastomer composition according to [1] above, wherein the melt mass flow rate of the propylene homopolymer B at 230 ° C. and a nominal load of 21.2 N is 1 to 30 g / 10 min.
[3] Further, propylene homopolymer D having a melt mass flow rate of 100 g / 10 min or more at 230 ° C. and a nominal load of 21.2 N is contained in an amount of 3 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic styrene elastomer A. The thermoplastic elastomer composition according to [2] above, wherein the content of the propylene homopolymer D is 1 to 80 parts by mass with respect to 100 parts by mass of the propylene homopolymer B.
[4] The thermoplastic elastomer composition according to the above [3], wherein the propylene homopolymer B has a z average molecular weight of 1,000,000 to 3,000,000.
[5] The thermoplastic elastomer composition according to any one of [1] to [4] above, wherein the thermoplastic styrene elastomer A has a weight average molecular weight of 50,000 to 500,000.
[6] The thermoplastic elastomer composition according to any one of [1] to [5] above, wherein the thermoplastic styrene elastomer A contains a controlled distribution type styrene block copolymer.
[7] The thermoplastic elastomer composition according to any one of [1] to [6] above, wherein the softener C contains at least one selected from paraffinic oils and naphthenic oils.
[8] The thermoplastic elastomer composition according to any one of [1] to [7] above, wherein the swell ratio of the thermoplastic elastomer composition is 1.1 to 2.5, and [9] the thermoplastic elastomer composition at 200 ° C., nominally. The thermoplastic elastomer composition according to any one of [1] to [8] above, wherein the melt mass flow rate under a load of 49 N is 6 to 30 g / 10 min.
　本発明の熱可塑性エラストマー組成物は、成形性及び機械的強度に優れ、フローマークの発生を最小限にすることが可能であるという効果を奏するものである。 The thermoplastic elastomer composition of the present invention has excellent moldability and mechanical strength, and has the effect of minimizing the occurrence of flow marks.
　本発明の熱可塑性エラストマー組成物は、熱可塑性スチレン系エラストマーＡとプロピレン単独重合体Ｂと軟化剤Ｃを含有するものであり、特定の分子量分布及びスウェル比を有するプロピレン単独重合体Ｂにより、成形時のフローマーク発生が改善される点に１つの特徴を有しており、詳細は不明なるも、以下のように推察される。
　フローマーク発生を改善するには樹脂流動時の流動末端の動きを安定化させる必要がある。樹脂のスウェル比を上げると、樹脂の広がろうとする力（第一法線応力）により、金型表面への転写が良くなり、フローマークが減少する。
　また、スウェル比を大きくするためには、分子同士の絡み合いが必要である。様々な長さを持った炭素鎖、つまり、広い分子量分布を有している方が、溶融混錬時の動きがランダムになり、コンパウンド時における分子同士の絡み合いが大きくなる。 The thermoplastic elastomer composition of the present invention contains a thermoplastic styrene elastomer A, a propylene homopolymer B, and a softening agent C, and is molded by a propylene homopolymer B having a specific molecular weight distribution and swell ratio. It has one feature in that the occurrence of flow marks at the time is improved, and although the details are unknown, it is presumed as follows.
In order to improve the occurrence of flow marks, it is necessary to stabilize the movement of the flow end during resin flow. When the swell ratio of the resin is increased, the force of the resin to spread (first normal stress) improves the transfer to the mold surface and reduces the flow mark.
In addition, in order to increase the swell ratio, it is necessary for the molecules to be entangled with each other. Carbon chains with various lengths, that is, those having a wide molecular weight distribution, have random movements during melt kneading, and the molecules are more entangled with each other during compounding.
　本発明における熱可塑性スチレン系エラストマーＡは、柔軟性と成形性の観点から、硬い部分（ハードセグメント）と柔らかい部分（ソフトセグメント）とから構成されていることが好ましく、ハードセグメントとしてスチレン系単量体からなる重合体のブロック単位（s1）と、ソフトセグメントとして共役ジエン化合物からなる重合体のブロック単位（b1）とを有するブロック共重合体（Z1）であることがより好ましい。 From the viewpoint of flexibility and moldability, the thermoplastic styrene-based elastomer A in the present invention is preferably composed of a hard portion (hard segment) and a soft portion (soft segment), and the styrene-based single amount as the hard segment. More preferably, it is a block copolymer (Z1) having a block unit (s1) of a polymer composed of a body and a block unit (b1) of a polymer composed of a conjugated diene compound as a soft segment.
　ブロック単位（s1）を構成するスチレン系単量体としては、スチレン、o-メチルスチレン、p-メチルスチレン、p-tert-ブチルスチレン、1,3-ジメチルスチレン、α-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。 Examples of the styrene-based monomer constituting the block unit (s1) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and the like. Examples include vinyl anthracene.
　ブロック共重合体（Z1）におけるブロック単位（s1）の含有量は、柔軟性の観点から、好ましくは10～50質量％、より好ましくは15～40質量％である。 From the viewpoint of flexibility, the content of the block unit (s1) in the block copolymer (Z1) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
　ブロック単位（b1）を構成する共役ジエン化合物としては、ブタジエン、イソプレン、1,3-ペンタジエン等が挙げられる。 Examples of the conjugated diene compound constituting the block unit (b1) include butadiene, isoprene, 1,3-pentadiene and the like.
　ブロック共重合体（Z1）は、水素添加することにより不飽和結合が減少し、耐熱性、耐候性及び機械的特性が向上することから、その一部又は全部が水素添加されていることが好ましい。水素添加率は、80％以上が好ましく、90％以上がより好ましい。本発明において、水素添加率は、ブロック共重合体中の共役ジエン化合物に由来する炭素－炭素二重結合の含有量を、水素添加の前後において、1H-NMRスペクトルによって測定し、該測定値から求めることができる。 The block copolymer (Z1) is preferably hydrogenated in part or in whole because unsaturated bonds are reduced by hydrogenation and heat resistance, weather resistance and mechanical properties are improved. .. The hydrogenation rate is preferably 80% or more, more preferably 90% or more. In the present invention, the hydrogenation rate is determined by measuring the content of carbon-carbon double bonds derived from the conjugated diene compound in the block copolymer before and after hydrogenation by 1H-NMR spectrum, and from the measured values. Can be sought.
　ブロック共重合体（Z1）の水素添加物の具体例としては、スチレン－エチレン・ブチレンブロック共重合体、スチレン－エチレン・ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレン・プロピレンブロック共重合体、スチレン－エチレン・プロピレン－スチレンブロック共重合体（ＳＥＰＳ）、スチレン－エチレン－エチレン・プロピレンブロック共重合体、スチレン－（エチレン－エチレン・プロピレン）－スチレンブロック共重合体（ＳＥＥＰＳ）、スチレン－イソブチレンブロック共重合体、スチレン－イソブチレン－スチレンブロック共重合体、（α-メチルスチレン）－エチレン・ブチレンブロック共重合体、（α-メチルスチレン）－エチレン・ブチレン－（α-メチルスチレン）ブロック共重合体等が挙げられる。これらは、単独であっても、2種以上の混合物であってもよいが、原料調製及び作業性の観点から、ＳＥＢＳ、ＳＥＰＳ、及びＳＥＥＰＳが好ましく、ＳＥＢＳがより好ましい。 Specific examples of the hydrogenated product of the block copolymer (Z1) include styrene-ethylene / butylene block copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene / propylene block copolymer. Combined, styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene / propylene block copolymer, styrene- (ethylene-ethylene / propylene) -styrene block copolymer (SEEPS), styrene- Isobutylene block copolymer, styrene-isobutylene-styrene block copolymer, (α-methylstyrene) -ethylene-butylene block copolymer, (α-methylstyrene) -ethylene-butylene- (α-methylstyrene) block Examples include polymers. These may be used alone or as a mixture of two or more kinds, but SEBS, SEPS, and SEEPS are preferable, and SEBS is more preferable, from the viewpoint of raw material preparation and workability.
　本発明において、熱可塑性スチレン系エラストマーＡは、耐熱性の観点から、〔ブロック単位（s1）－ブロック単位（b1）〕型のジブロック共重合体よりも〔ブロック単位（s1）－ブロック単位（b1）－ブロック単位（s1）〕型のトリブロック共重合体が好ましい。前記水素添加物のなかで、トリブロック共重合体としては、ＳＥＢＳ、ＳＥＰＳ、ＳＥＥＰＳ、ＳＥＢ（Ｓ）Ｓ、スチレン－イソブチレン－スチレンブロック共重合体、（α-メチルスチレン）－エチレン・ブチレン－（α-メチルスチレン）ブロック共重合体等が挙げられる。 In the present invention, the thermoplastic styrene-based elastomer A is more [block unit (s1) -block unit (b1)] than the [block unit (s1) -block unit (b1)] type diblock copolymer from the viewpoint of heat resistance. b1) -block unit (s1)] type triblock copolymers are preferred. Among the hydrogenated additives, the triblock copolymers include SEBS, SEPS, SEEPS, SEB (S) S, styrene-isobutylene-styrene block copolymer, (α-methylstyrene) -ethylene-butylene- ( Examples thereof include α-methylstyrene) block copolymers.
　トリブロック共重合体の含有量は、スチレン系ブロック共重合体Ａ中、好ましくは80質量％以上、より好ましくは90質量％以上、さらに好ましくは95質量％以上である。 The content of the triblock copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more in the styrene-based block copolymer A.
　熱可塑性スチレン系エラストマーＡは、さまざまな特性のものが工業的に大量に生産されていて入手しやすい観点から、酸変性されていないことが好ましい。 The thermoplastic styrene-based elastomer A is preferably not acid-modified from the viewpoint that those having various properties are industrially mass-produced and easily available.
　なお、熱可塑性スチレン系エラストマーＡは、制御分布型スチレン系ブロック共重合体であってもよい。制御分布型スチレン系ブロック共重合体としては、ブロック単位（b1）の代わりに、共役ジエンとスチレン系単量体との共重合単位であり、制御分布構造を有するブロック単位（b1’）を有するものが好ましい。 The thermoplastic styrene-based elastomer A may be a controlled distribution type styrene-based block copolymer. The controlled distribution type styrene block copolymer is a copolymer unit of a conjugated diene and a styrene monomer instead of the block unit (b1), and has a block unit (b1') having a controlled distribution structure. Is preferable.
　ブロック単位（b1’）は、共役ジエン単位を主要構成単位として含有する領域を2個以上、スチレン系単量体単位を主要構成単位として含有する領域を1個以上有し、ブロック単位（s1）に隣接する両末端は共役ジエン単位を主要構成単位として含有する領域であることが好ましい。 The block unit (b1') has two or more regions containing a conjugated diene unit as a main constituent unit and one or more regions containing a styrene-based monomer unit as a main constituent unit, and is a block unit (s1). Both ends adjacent to are preferably regions containing a conjugated diene unit as a main constituent unit.
　制御分布型スチレン系ブロック共重合体Ａにおけるスチレン系単量体単位の含有量は、極性樹脂との熱融着性の観点から、好ましくは45～80質量％、より好ましくは50～75質量％、さらに好ましくは55～70質量％である。制御分布型スチレン系ブロック共重合体Ａにおけるスチレン系単量体単位の含有量は、ハードセグメントのスチレン系単量体単位とソフトセグメント中のスチレン系単量体単位の合計量とする。 The content of the styrene-based monomer unit in the controlled distribution type styrene-based block copolymer A is preferably 45 to 80% by mass, more preferably 50 to 75% by mass, from the viewpoint of heat-sealing property with the polar resin. , More preferably 55-70% by mass. The content of the styrene-based monomer unit in the controlled distribution type styrene-based block copolymer A is the total amount of the styrene-based monomer unit in the hard segment and the styrene-based monomer unit in the soft segment.
　なお、制御分布型スチレン系エラストマーブロック共重合体は、当該技術分野において周知のものであり、例えば、特開２００７－８４８２１号公報、特表２０１３－５１８１７０号公報等に記載されている。 Note that the controlled distribution type styrene-based elastomer block copolymer is well known in the art, and is described in, for example, Japanese Patent Application Laid-Open No. 2007-84421 and Japanese Patent Application Laid-Open No. 2013-518170.
　熱可塑性スチレン系エラストマーＡの重量平均分子量は、耐オイルブリード性、耐熱性及び機械特性の観点から、好ましくは50,000以上、より好ましくは100,000以上、さらに好ましくは200,000以上であり、加熱時の流れやすさ、つまり製造時における成形性の観点から、好ましくは500,000以下、より好ましくは400,000以下、さらに好ましくは300,000以下である。熱可塑性スチレン系エラストマーＡが複数のエラストマーからなる場合は、各エラストマーの重量平均分子量の加重平均値が上記範囲内に入ることが好ましい。 The weight average molecular weight of the thermoplastic styrene-based elastomer A is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 200,000 or more, and easy to flow during heating, from the viewpoints of oil bleed resistance, heat resistance and mechanical properties. That is, from the viewpoint of moldability at the time of manufacture, it is preferably 500,000 or less, more preferably 400,000 or less, and further preferably 300,000 or less. When the thermoplastic styrene-based elastomer A is composed of a plurality of elastomers, it is preferable that the weighted average value of the weight average molecular weight of each elastomer falls within the above range.
　熱可塑性エラストマー組成物中の熱可塑性スチレン系エラストマーＡの含有量は、好ましくは20～70質量％、より好ましくは30～60質量％である。 The content of the thermoplastic styrene-based elastomer A in the thermoplastic elastomer composition is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
　なお、熱可塑性スチレン系エラストマーＡは、1種からなるものであっても、2種以上が併用されていてもあってもよく、後述のプロピレン単独重合体Ｂ及び軟化剤Ｃについても同様である。 The thermoplastic styrene-based elastomer A may be composed of one type or two or more types may be used in combination, and the same applies to the propylene homopolymer B and the softening agent C described later. ..
　本発明におけるプロピレン単独重合体Ｂは、一般にはホモポリプロピレン樹脂と呼ばれている。ホモポリプロピレン樹脂以外のプロピレン系重合体としては、他にも、ブロックポリプロピレンやランダムポリプロピレン等がある。これらは、本発明の効果を損なわない範囲で、熱可塑性エラストマー組成物に含まれていてもよい。また、プロピレン単独重合体Ｂとして、2種以上のプロピレン単独重合体が併用されていてもよい。 The propylene homopolymer B in the present invention is generally called a homopolypropylene resin. Other propylene-based polymers other than the homopolypropylene resin include block polypropylene, random polypropylene, and the like. These may be contained in the thermoplastic elastomer composition as long as the effect of the present invention is not impaired. Further, as the propylene homopolymer B, two or more kinds of propylene homopolymers may be used in combination.
　ポリプロピレン単独重合体Ｂは、既存のスラリープロセス（液体モノマー中の重合）や気相重合等の方法により得られる。また、各後続の重合が直前の重合反応中に形成された重合性物質の存在下で行われる少なくとも２の逐次重合ステージを具備する逐次重合方法により得られたものであってもよい。重合は、立体特異的チーグラーナッタ（Ziegler-Natta）触媒の存在下で行われることが好ましい。具体的には、（Ａ）マグネシウム、チタン、ハロゲン、及びスクシネート系化合物から選択される電子供与体化合物を必須成分として含有する固体触媒；（Ｂ）有機アルミニウム化合物；及び必要に応じて（Ｃ）ケイ素化合物から選択される外部電子供与体化合物を含む触媒成分の存在下で行われる方法が挙げられる。上記立体特異的チーグラーナッタ触媒は、特許文献等により周知の触媒である。 Polypropylene homopolymer B can be obtained by an existing slurry process (polymerization in a liquid monomer), gas phase polymerization, or the like. Further, each subsequent polymerization may be obtained by a step-growth polymerization method comprising at least two step-growth polymerization stages in which the subsequent polymerization is carried out in the presence of a polymerizable substance formed during the immediately preceding polymerization reaction. The polymerization is preferably carried out in the presence of a stereospecific Ziegler-Natta catalyst. Specifically, a solid catalyst containing (A) an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component; (B) an organoaluminum compound; and, if necessary, (C). Examples thereof include methods performed in the presence of a catalytic component containing an external electron donor compound selected from silicon compounds. The stereospecific Ziegler-Natta catalyst is a catalyst well known in patent documents and the like.
　プロピレン単独重合体Ｂのスウェル比は、1.1～2.5であり、好ましくは、1.2～2.0である。スウェル比が1.1未満であると、フローマークが発生しやすくなる傾向にあり、2.5を超えると、汎用的な製造プロセスにおいて安価に製造することが困難となる傾向にある。プロピレン単独重合体Ｂが2種以上のプロピレン単独重合体からなる場合は、それぞれのプロピレン単独重合体のスウェル比が上記範囲内であることが好ましい。後述の平均分子量等の物性についても同様である。 The swell ratio of the propylene homopolymer B is 1.1 to 2.5, preferably 1.2 to 2.0. If the swell ratio is less than 1.1, flow marks tend to occur, and if it exceeds 2.5, it tends to be difficult to manufacture at low cost in a general-purpose manufacturing process. When the propylene homopolymer B is composed of two or more kinds of propylene homopolymers, it is preferable that the swell ratio of each propylene homopolymer is within the above range. The same applies to the physical characteristics such as the average molecular weight described later.
　プロピレン単独重合体Ｂの重量平均分子量と数平均分子量の比（重量平均分子量／数平均分子量）は、10.0～25.0であり、好ましくは11.0～24.0である。分子量分布が10.0未満であると、フローマークの改善効果が劣り、一方、25.0を超えると、製造が困難になる。ここで、重量平均分子量と数平均分子量の比（重量平均分子量／数平均分子量）は、分子量分布の指標であり、この比が大きいほど、分子量分布が広いことを意味する。 The ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) of the propylene homopolymer B is 10.0 to 25.0, preferably 11.0 to 24.0. If the molecular weight distribution is less than 10.0, the effect of improving the flow mark is inferior, while if it exceeds 25.0, production becomes difficult. Here, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is an index of the molecular weight distribution, and the larger the ratio, the wider the molecular weight distribution.
　プロピレン単独重合体Ｂの重量平均分子量は、機械特性の観点から、好ましくは350,000以上、より好ましくは400,000以上であり、また、好ましくは550,000以下、より好ましくは500,000以下である。 The weight average molecular weight of the propylene homopolymer B is preferably 350,000 or more, more preferably 400,000 or more, and preferably 550,000 or less, more preferably 500,000 or less, from the viewpoint of mechanical properties.
　プロピレン単独重合体Ｂのｚ平均分子量は、比較的広い分子量分布を有することから、好ましくは1,000,000以上、より好ましくは1,500,000以上であり、また、好ましくは3,000,000以下、より好ましくは2,000,000以下である。 Since the propylene homopolymer B has a relatively wide molecular weight distribution, the z average molecular weight is preferably 1,000,000 or more, more preferably 1,500,000 or more, and preferably 3,000,000 or less, more preferably 2,000,000 or less.
　プロピレン単独重合体Ｂは、熱可塑性エラストマー組成物の分散性及び成形性の観点から流動性が高い方が好ましい。流動性はメルトマスフローレイト（ＭＦＲ）によって評価することができ、230℃、公称荷重21.2Ｎで、好ましくは0.1g/10min以上、より好ましくは1g/10min以上であり、組成物の製造工程での混錬のしやすさから、好ましくは50g/10min以下、より好ましくは40g/10min以下、さらに好ましくは30g/10min以下、さらに好ましくは15g/10min以下である。 The propylene homopolymer B preferably has high fluidity from the viewpoint of dispersibility and moldability of the thermoplastic elastomer composition. The fluidity can be evaluated by melt mass flow rate (MFR) and is 230 ° C., nominal load 21.2 N, preferably 0.1 g / 10 min or higher, more preferably 1 g / 10 min or higher, in the process of manufacturing the composition. From the viewpoint of ease of kneading, it is preferably 50 g / 10 min or less, more preferably 40 g / 10 min or less, further preferably 30 g / 10 min or less, still more preferably 15 g / 10 min or less.
　プロピレン単独重合体Ｂの含有量は、熱可塑性スチレン系エラストマーＡ 100質量部に対して、成形性の観点から、10質量部以上、好ましくは30質量部以上であり、柔軟性の観点から、400質量部以下、好ましくは300質量部以下、より好ましくは100質量部以下である。 The content of the propylene homopolymer B is 10 parts by mass or more, preferably 30 parts by mass or more from the viewpoint of moldability with respect to 100 parts by mass of the thermoplastic styrene elastomer A, and 400 by mass from the viewpoint of flexibility. It is by mass or less, preferably 300 parts by mass or less, and more preferably 100 parts by mass or less.
　また、熱可塑性エラストマー組成物中のプロピレン単独重合体Ｂの含有量は、好ましくは5～60質量％、より好ましくは10～40質量％、さらに好ましくは10～20質量部である。 The content of the propylene homopolymer B in the thermoplastic elastomer composition is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 20 parts by mass.
　軟化剤Ｃは、例えば、パラフィン系オイル、ナフテン系オイル、芳香族系オイル等のゴム用軟化剤が挙げられるが、これらのなかでは、熱可塑性スチレン系エラストマーとの親和性が良好で、ブリードが起きにくいという観点から、パラフィン系オイル及びナフテン系オイルから選択される少なくとも1種が好ましく、パラフィン系オイルがより好ましい。 Examples of the softening agent C include softening agents for rubber such as paraffin-based oils, naphthen-based oils, and aromatic oils. Among these, softeners C have good affinity with thermoplastic styrene-based elastomers and bleed. From the viewpoint of being less likely to occur, at least one selected from paraffin-based oil and naphthen-based oil is preferable, and paraffin-based oil is more preferable.
　軟化剤Ｃの40℃での動粘度は、高い方が加熱溶融時の揮発を防ぎ、耐ブリード性も良くなることから、好ましくは30mm2/s以上、より好ましくは60mm2/s以上、さらに好ましくは80mm2/s以上であり、低い方が取扱いが容易であることから、好ましくは500mm2/s以下、より好ましくは350mm2/s以下、さらに好ましくは200mm2/s以下である。 The higher the kinematic viscosity of the softener C at 40 ° C., the more it prevents volatilization during heating and melting, and the better the bleed resistance. Therefore, it is preferably 30 mm 2 / s or more, more preferably 60 mm 2 / s or more, and further. It is preferably 80 mm 2 / s or more, and the lower one is easier to handle. Therefore, it is preferably 500 mm 2 / s or less, more preferably 350 mm 2 / s or less, and further preferably 200 mm 2 / s or less.
　軟化剤Ｃの含有量は、熱可塑性スチレン系エラストマーＡ 100質量部に対して、柔軟性の観点から、10質量部以上、好ましくは50質量部以上であり、オイルブリード抑制の観点から、300質量部以下、好ましくは150質量部以下である。 The content of the softener C is 10 parts by mass or more, preferably 50 parts by mass or more from the viewpoint of flexibility, and 300 parts by mass from the viewpoint of suppressing oil bleeding, with respect to 100 parts by mass of the thermoplastic styrene elastomer A. Parts or less, preferably 150 parts by mass or less.
　また、熱可塑性エラストマー組成物中の軟化剤Ｃの含有量は、好ましくは5～65質量％、より好ましくは20～50質量％である。 Further, the content of the softening agent C in the thermoplastic elastomer composition is preferably 5 to 65% by mass, more preferably 20 to 50% by mass.
　本発明の熱可塑性エラストマー組成物は、組成物の流動性を高め、成形性を向上さえる観点から、プロピレン単独重合体Ｂよりも、流動性の高い、即ちメルトマスフローレイトの大きいプロピレン単独重合体Ｄを、さらに含有することが好ましい。 The thermoplastic elastomer composition of the present invention has a higher fluidity than the propylene homopolymer B, that is, a propylene homopolymer D having a large melt mass flow rate, from the viewpoint of increasing the fluidity of the composition and improving the moldability. It is preferable to further contain.
　プロピレン単独重合体Ｄの、230℃、公称荷重21.2Ｎでのメルトマスフローレイト（ＭＦＲ）は、100g/10min以上が好ましく、より好ましくは500g/10min以上、さらに好ましくは1000g/10min以上であり、また、好ましくは5000g/10min以下、より好ましくは3000g/10min以下である。 The melt mass flow rate (MFR) of the propylene homopolymer D at 230 ° C. and a nominal load of 21.2 N is preferably 100 g / 10 min or more, more preferably 500 g / 10 min or more, still more preferably 1000 g / 10 min or more, and also. It is preferably 5000 g / 10 min or less, and more preferably 3000 g / 10 min or less.
　プロピレン単独重合体Ｄのスウェル比は、好ましくは0.4～1.0、より好ましくは0.6～0.8である。 The swell ratio of the propylene homopolymer D is preferably 0.4 to 1.0, more preferably 0.6 to 0.8.
　プロピレン単独重合体Ｄの重量平均分子量と数平均分子量の比（重量平均分子量／数平均分子量）は、好ましくは1～15、より好ましくは5～10である。 The ratio of the weight average molecular weight to the number average molecular weight of the propylene homopolymer D (weight average molecular weight / number average molecular weight) is preferably 1 to 15, more preferably 5 to 10.
　プロピレン単独重合体Ｄの重量平均分子量は、好ましくは7,000以上、より好ましくは10,000以上であり、また、好ましくは150,000以下、より好ましくは120,000以下である。 The weight average molecular weight of the propylene homopolymer D is preferably 7,000 or more, more preferably 10,000 or more, and preferably 150,000 or less, more preferably 120,000 or less.
　プロピレン単独重合体Ｄのｚ平均分子量は、機械特性の観点から、好ましくは30,000以上、より好ましくは100,000以上であり、また、好ましくは350,000以下、より好ましくは300,000以下である。 From the viewpoint of mechanical properties, the z average molecular weight of the propylene homopolymer D is preferably 30,000 or more, more preferably 100,000 or more, and preferably 350,000 or less, more preferably 300,000 or less.
　フローマーク改善の観点から、プロピレン単独重合体Ｄの含有量は、プロピレン単独重合体Ｂの含有量以下であることが好ましく、プロピレン単独重合体Ｂ 100質量部に対する、プロピレン単独重合体Ｄの含有量は、好ましくは1～100質量部、さらに好ましくは1～80質量部、さらに好ましくは20～50質量部である。 From the viewpoint of improving the flow mark, the content of the propylene homopolymer D is preferably equal to or less than the content of the propylene homopolymer B, and the content of the propylene homopolymer D with respect to 100 parts by mass of the propylene homopolymer B. Is preferably 1 to 100 parts by mass, more preferably 1 to 80 parts by mass, still more preferably 20 to 50 parts by mass.
　プロピレン単独重合体Ｄの含有量は、熱可塑性スチレン系エラストマーＡ 100質量部に対して、成形性の観点から、好ましくは3質量部以上、より好ましくは5質量部以上であり、また、好ましくは400質量部以下、より好ましくは200質量部以下、さらに好ましくは100質量部以下である。 The content of the propylene homopolymer D is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of the thermoplastic styrene elastomer A from the viewpoint of moldability. It is 400 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less.
　また、熱可塑性エラストマー組成物中のプロピレン単独重合体Ｄの含有量は、本発明の熱可塑性エラストマー組成物中、好ましくは1～40質量％である。 Further, the content of the propylene homopolymer D in the thermoplastic elastomer composition is preferably 1 to 40% by mass in the thermoplastic elastomer composition of the present invention.
　本発明の熱可塑性エラストマー組成物は、さらに安定剤を含有していてもよい。樹脂組成物の安定剤は各種知られているが、本発明においては、耐熱老化性が向上する観点からは酸化防止剤が、また、耐候性が向上する観点からは紫外線吸収剤及び光安定剤が、それぞれ好ましい。 The thermoplastic elastomer composition of the present invention may further contain a stabilizer. Various stabilizers of the resin composition are known, but in the present invention, an antioxidant is used from the viewpoint of improving heat aging resistance, and an ultraviolet absorber and a light stabilizer are used from the viewpoint of improving weather resistance. However, each is preferable.
　本発明の熱可塑性エラストマー組成物は、本発明の効果を損なわない範囲で、他の熱可塑性樹脂や熱可塑性エラストマーを含有していてもよい。 The thermoplastic elastomer composition of the present invention may contain other thermoplastic resins or thermoplastic elastomers as long as the effects of the present invention are not impaired.
　本発明の熱可塑性エラストマー組成物は、本発明の効果を損なわない範囲で、さらに、カーボンブラック、シリカ、炭素繊維、ガラス繊維等の補強剤；炭酸カルシウム、タルク、クレー、酸化チタン、マイカ等の充填剤、絶縁性熱伝導性フィラー、滑剤、顔料、難燃剤、帯電防止剤、離型剤、粘着付与剤、架橋剤、架橋助剤、発泡剤、香料等の各種添加剤を含有していてもよい。 The thermoplastic elastomer composition of the present invention is a reinforcing agent for carbon black, silica, carbon fiber, glass fiber, etc., as long as the effect of the present invention is not impaired; calcium carbonate, talc, clay, titanium oxide, mica, etc. It contains various additives such as fillers, insulating heat conductive fillers, talc, pigments, flame retardants, antistatic agents, mold release agents, tackifiers, cross-linking agents, cross-linking aids, foaming agents, and fragrances. May be good.
　本発明の熱可塑性エラストマー組成物は、熱可塑性スチレン系エラストマーＡ、プロピレン単独重合体Ｂ、及び軟化剤Ｃと、さらに必要に応じて、プロピレン単独重合体Ｄ、酸化防止剤等の添加剤を適宜混合し、冷却により固化させて得られる。 In the thermoplastic elastomer composition of the present invention, a thermoplastic styrene elastomer A, a propylene homopolymer B, and a softening agent C, and if necessary, additives such as a propylene homopolymer D and an antioxidant are appropriately added. It is obtained by mixing and solidifying by cooling.
　本発明でいう「混合」とは、各種原料が良好に混合される方法であれば特に限定されず、各種原料を溶解可能な有機溶媒中に溶解させて混合してもよいし、溶融混練によって混合してもよいが、原料の混合は、各原料が溶融する条件下で行うことが好ましい。 The term "mixing" as used in the present invention is not particularly limited as long as it is a method in which various raw materials are mixed well, and various raw materials may be dissolved in a soluble organic solvent and mixed, or by melt kneading. Although they may be mixed, it is preferable to mix the raw materials under the condition that the raw materials are melted.
　溶融混練する場合には、一般的な押出機を用いることができ、混練状態の向上のため、二軸の押出機を使用することが好ましい。押出機への供給は、予めヘンシェルミキサー等の混合装置を用いて各種成分を混合したものを一つのホッパーから供してもよいし、二つのホッパーにそれぞれの成分を仕込みホッパー下のスクリュー等で定量しながら供してもよい。 In the case of melt-kneading, a general extruder can be used, and it is preferable to use a twin-screw extruder in order to improve the kneading state. For supply to the extruder, a mixture of various components using a mixing device such as a Henschel mixer in advance may be supplied from one hopper, or each component is charged into two hoppers and quantified with a screw or the like under the hopper. You may serve while.
　熱可塑性エラストマー組成物を構成する原料を混合して得られる生成物は、用途に応じて、ペレット、粉体、シート等の形状とすることができる。例えば、押出機によって溶融混練してストランドに押出し、冷水中で冷却しつつカッターによって円柱状や米粒状等のペレットに切断される。得られたペレットは、通常、射出成形、押出成形によって所定のシート状成形品や金型成形品とする。また、溶融混練物をルーダー等でペレットにし成形加工原料とすることもできる。シート状の熱可塑性エラストマー組成物に、台紙等を貼付した中間製品としてもよい。 The product obtained by mixing the raw materials constituting the thermoplastic elastomer composition can be in the form of pellets, powders, sheets, etc., depending on the application. For example, it is melt-kneaded by an extruder and extruded into a strand, and while being cooled in cold water, it is cut into pellets such as columns and rice granules by a cutter. The obtained pellets are usually made into a predetermined sheet-shaped molded product or mold-molded product by injection molding or extrusion molding. Further, the melt-kneaded product can be pelletized with a ruder or the like and used as a raw material for molding. It may be an intermediate product in which a mount or the like is attached to a sheet-shaped thermoplastic elastomer composition.
　本発明の熱可塑性エラストマー組成物の硬度は、柔軟性の観点から、Ａ硬度で、好ましくは30以上、より好ましくは40以上、さらに好ましくは50以上であり、Ａ硬度が90を超える場合は、Ｄ硬度で測定することとし、熱可塑性エラストマー組成物の硬度の上限は、Ｄ硬度で、好ましくは60以下、より好ましくは40以下、Ａ硬度で、好ましくは90以下、より好ましくは80以下である。 From the viewpoint of flexibility, the hardness of the thermoplastic elastomer composition of the present invention is A hardness, preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, and when the A hardness exceeds 90, The upper limit of the hardness of the thermoplastic elastomer composition is D hardness, preferably 60 or less, more preferably 40 or less, and A hardness, preferably 90 or less, more preferably 80 or less. ..
　本発明の熱可塑性エラストマー組成物の200℃、公称荷重49Ｎでのメルトマスフローレイトは、流動性及び成形性の観点から、6～30g/10minが好ましく、10～20g/10minがより好ましい。 The melt mass flow rate of the thermoplastic elastomer composition of the present invention at 200 ° C. and a nominal load of 49 N is preferably 6 to 30 g / 10 min, more preferably 10 to 20 g / 10 min, from the viewpoint of fluidity and moldability.
　本発明の熱可塑性エラストマー組成物のスウェル比は、好ましくは1.1～2.5、より好ましくは、1.2～2.0である。 The swell ratio of the thermoplastic elastomer composition of the present invention is preferably 1.1 to 2.5, more preferably 1.2 to 2.0.
　本発明の熱可塑性エラストマー組成物を、常法に従って、適宜加熱成形することにより、成形体が得られる。成形体の製造に用いられる装置には、成形材料を溶融できる任意の成形機を用いることができ、例えば、ニーダー、押出成形機、射出成形機、プレス成形機、ブロー成形機、ミキシングロール等が挙げられる。 A molded product can be obtained by appropriately heat-molding the thermoplastic elastomer composition of the present invention according to a conventional method. Any molding machine capable of melting the molding material can be used as the apparatus used for manufacturing the molded body, for example, a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, a mixing roll and the like. Can be mentioned.
　本発明の熱可塑性エラストマー組成物を加熱成形して得られる成形体の用途は、特に限定されるものではなく一般的なスチレン系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、アクリル系エラストマーやポリエステル系エラストマー等が用いられる分野に用いることができる。 The application of the molded product obtained by heat-molding the thermoplastic elastomer composition of the present invention is not particularly limited, and general styrene-based elastomer, polyolefin-based elastomer, polyurethane-based elastomer, polyamide-based elastomer, and acrylic-based elastomer. It can be used in fields where or polyester elastomers are used.
　以下に、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よってなんら限定されるものではない。実施例及び比較例で使用した原料の各種物性は、以下の方法により測定した。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Various physical properties of the raw materials used in Examples and Comparative Examples were measured by the following methods.
＜成分Ａ：熱可塑性スチレン系エラストマー＞
〔スチレン系単量体単位の含有量〕
　核磁気共鳴装置（ドイツ国BRUKER社製、DPX-400）によって、プロトンNMR測定を行い、スチレンの特性基の定量を行うことによってスチレン及び／又はスチレン誘導体の含有量を決定する。他の単量体単位の含有量もプロトンNMR測定により求めることができる。 <Component A: Thermoplastic Styrene Elastomer>
[Content of styrene-based monomer unit]
The content of styrene and / or styrene derivative is determined by performing proton NMR measurement with a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400) and quantifying the characteristic group of styrene. The content of other monomer units can also be determined by proton NMR measurement.
〔重量平均分子量（Mw）〕
　以下の測定条件で、ゲルパーミエーションクロマトグラフにより、ポリスチレン換算で分子量を測定し、重量平均分子量を求める。 [Weight average molecular weight (Mw)]
Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by a gel permeation chromatograph to determine the weight average molecular weight.
測定装置
・ポンプ：JASCO（日本分光（株））製、PU-980
・カラムオーブン：昭和電工（株）製、AO-50
・検出器：日立製、RI（示差屈折計）検出器 L-3300
・カラム種類：昭和電工（株）製「K-805L（8.0×300mm）」及び「K-804L（8.0×300mm）」各１本を直列使用
・カラム温度：40℃
・ガードカラム：K-G（4.6×10mm）
・溶離液：クロロホルム
・溶離液流量：1.0ml/min
・試料濃度：約1mg/ml
・試料溶液ろ過：ポリテトラフルオロエチレン製0.45μm孔径ディスポーザブルフィルタ
・検量線用標準試料：昭和電工（株）製ポリスチレン Measuring device / pump: JASCO (JASCO Corporation), PU-980
・ Column oven: Showa Denko KK, AO-50
・ Detector: Hitachi, RI (differential refractometer) detector L-3300
-Column type: Showa Denko Corporation "K-805L (8.0 x 300 mm)" and "K-804L (8.0 x 300 mm)" are used in series.-Column temperature: 40 ° C
・ Guard column: KG (4.6 x 10 mm)
・ Eluent: Chloroform ・ Eluent flow rate: 1.0 ml / min
・ Sample concentration: Approximately 1 mg / ml
・ Sample solution filtration: Polytetrafluoroethylene 0.45 μm pore size disposable filter ・ Standard sample for calibration curve: Polystyrene manufactured by Showa Denko KK
＜成分Ｂ及び成分Ｄ：プロピレン単独重合体等＞
〔スウェル比〕
　キャピラリーレオメータ（（株）東洋精機製作所、キャピログラフグラフ1D）を用い、200℃、せん断速度100（1／sec）、オリフィス直径2.0mmで押し出された試料のストランド径をノギスで測定し、ストランド直径をオリフィス直径で除した数値をスウェル比とする。 <Component B and Component D: Propylene homopolymer, etc.>
[Swell ratio]
Using a capillary rheometer (Toyo Seiki Seisakusho Co., Ltd., Capillograph Graph 1D), measure the strand diameter of an extruded sample at 200 ° C., shear rate 100 (1 / sec), and orifice diameter 2.0 mm with a caliper, and perform strands. The swell ratio is the value obtained by dividing the diameter by the orifice diameter.
〔メルトマスフローレイト（ＭＦＲ）〕
　ASTM D1238に準拠して、230℃、公称荷重21.2Ｎの条件で測定する。 [Melt Mass Flow Rate (MFR)]
Measured according to ASTM D1238 under the conditions of 230 ° C. and nominal load 21.2N.
〔平均分子量及び分子量分布〕
　ゲルパーミエーションクロマトグラフにより、ポリスチレン換算で分子量を測定し、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、及びｚ平均分子量（Ｍｚ）を求め、分子量分布（Ｍｗ／Ｍｎ）を算出する。
・GPC装置：GPCV2000システム（Waters Allince）
・ガードカラム：GPC UT-G（Shodex）
・分析カラム：GPC UT-807+GPC UT-806M×2（Shodex）
・カラム温度：140℃
・溶離液：0.1w/v％BHT含有高速液体クロマトグラフ用オルトジクロロベンゼン
・溶離液流量：1.0mL/min
・試料濃度：約0.8mg/mL
・試料溶液ろ過：PTFE製0.5μm孔径メンブレンフィルター
・注入量：317μL
・標準試料：標準ポリスチレン（Shodex STANDARD）
　　　　　　分子量：7.30×106，3.85×106，2.06×106，6.66×105，1.33×105，
　　　　　　　　　　5.51×104，2.86×104，7.20×103，2.94×103
　　　　　　ポリスチレンMp370 (Agilent Technologies)
　　　　　　分子量：3.70×102 [Average molecular weight and molecular weight distribution]
The molecular weight is measured in terms of polystyrene by a gel permeation chromatograph, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the z average molecular weight (Mz) are obtained, and the molecular weight distribution (Mw / Mn) is calculated.
・ GPC device: GPCV2000 system (Waters Allince)
・ Guard column: GPC UT-G (Shodex)
-Analytical column: GPC UT-807 + GPC UT-806M x 2 (Shodex)
・ Column temperature: 140 ℃
・ Eluent: Orthodichlorobenzene for high performance liquid chromatography containing 0.1w / v% BHT ・ Eluent flow rate: 1.0mL / min
・ Sample concentration: Approximately 0.8 mg / mL
・ Sample solution filtration: PTFE 0.5 μm pore size membrane filter ・ Injection volume: 317 μL
-Standard sample: Standard polystyrene (Shodex STANDARD)
Molecular weight: 7.30 × 10 6 , 3.85 × 10 6 , 2.06 × 10 6 , 6.66 × 10 5 , 1.33 × 10 5 ,
5.51 × 10 4 , 2.86 × 10 4 , 7.20 × 10 3 , 2.94 × 10 3
Polystyrene Mp370 (Agilent Technologies)
Molecular weight: 3.70 × 10 2
＜成分Ｃ：軟化剤＞
〔動粘度〕
　JIS Z 8803に従って、40℃の温度で測定する。 <Component C: Softener>
[Kinematic viscosity]
Measure at a temperature of 40 ° C according to JIS Z 8803.
実施例１～１１及び比較例１～９
（1）　熱可塑性エラストマー組成物（ペレット）の作製
　軟化剤以外の表６～８に示す材料をドライブレンドした後、これに軟化剤を含浸させて混合物を作製した。その後、混合物を下記の条件で、押出機で溶融混練して、ストランドに押出し、冷水中で冷却しつつカッターによって、直径3mm程度、厚さ3mm程度に切断し、熱可塑性エラストマー組成物のペレットを製造した。 Examples 1 to 11 and Comparative Examples 1 to 9
(1) Preparation of Thermoplastic Elastomer Composition (Pellet) The materials shown in Tables 6 to 8 other than the softener were dry-blended and then impregnated with the softener to prepare a mixture. Then, the mixture is melt-kneaded with an extruder under the following conditions, extruded into strands, and cut into a diameter of about 3 mm and a thickness of about 3 mm with a cutter while being cooled in cold water to obtain pellets of the thermoplastic elastomer composition. Manufactured.
〔溶融混練条件〕
押出機：KZW32TW-60MG-NH（商品名、(株)テクノベル製）
シリンダー温度：180～220℃
スクリュー回転数：300r/min [Melting and kneading conditions]
Extruder: KZW32TW-60MG-NH (trade name, manufactured by Technobel Co., Ltd.)
Cylinder temperature: 180-220 ℃
Screw rotation speed: 300r / min
　実施例及び比較例で使用した表６～８に記載の原料の詳細は以下の通り。 Details of the raw materials shown in Tables 6 to 8 used in Examples and Comparative Examples are as follows.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
(2)　熱可塑性エラストマー組成物の成形体の作製
　ペレットを、下記の条件で射出成形し、厚さ2mm×幅125mm×長さ125mmのプレートを作製した。 (2) Preparation of Molded Body of Thermoplastic Elastomer Composition Pellets were injection-molded under the following conditions to prepare a plate having a thickness of 2 mm, a width of 125 mm and a length of 125 mm.
〔射出成形条件〕
射出成形機：射出成形機：EC100SX II-4B（東芝機械（株)製）
射出成形温度：200℃
射出圧力：120MPa　保圧30MPa
射出時間：2sec
金型温度：40℃ [Injection molding conditions]
Injection molding machine: Injection molding machine: EC100SX II-4B (manufactured by Toshiba Machine Co., Ltd.)
Injection molding temperature: 200 ° C
Injection pressure: 120MPa Holding pressure 30MPa
Injection time: 2sec
Mold temperature: 40 ℃
　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について、前記ペレット又はプレートを用い、下記の評価を行った。結果を表６～８に示す。 The thermoplastic elastomer compositions obtained in Examples and Comparative Examples were evaluated as follows using the pellets or plates. The results are shown in Tables 6-8.
〔柔軟性〕
(1)　Ａ硬度
　プレートを3枚重ね（合計6mm）としたものについて、JIS K 6253に準拠した測定時間1秒のＡ硬度（試験開始から1秒後の値）を測定した。測定は温度23℃、湿度50％の室内で1日状態調節の後、実施した。 [Flexibility]
(1) A hardness A hardness (value 1 second after the start of the test) was measured for a measurement time of 1 second in accordance with JIS K 6253 for a stack of 3 A hardness plates (total 6 mm). The measurement was carried out after adjusting the condition for one day in a room with a temperature of 23 ° C and a humidity of 50%.
(2)　Ｄ硬度
　プレートを3枚重ね（合計6mm）としたものについて、JIS K 6253に準拠した測定時間1秒のＤ硬度（試験開始から1秒後の値）を測定した。測定は温度23℃、湿度50％の室内で1日状態調節の後、実施した。 (2) D-hardness The D-hardness (value 1 second after the start of the test) was measured for a measurement time of 1 second in accordance with JIS K 6253 for a stack of 3 plates (6 mm in total). The measurement was carried out after adjusting the condition for one day in a room with a temperature of 23 ° C and a humidity of 50%.
〔機械的強度（引張破断強度）〕
　プレートから、型抜機を用いてJIS K7113に記載の3号試験片を作製し、（株）島津製作所製の引張試験機（オートグラフ AG-50kND型）を用いて、23℃の温度環境下、200mm/minの速度で試験片を引っ張った。試験片破断時の応力（MPa）を破断強度として記録した。破断強度が大きいほど、機械的強度が良好である。 [Mechanical strength (tensile breaking strength)]
From the plate, use a die-cutting machine to prepare the No. 3 test piece described in JIS K7113, and use a tensile tester (Autograph AG-50kND type) manufactured by Shimadzu Corporation under a temperature environment of 23 ° C. The test piece was pulled at a speed of 200 mm / min. The stress (MPa) at break of the test piece was recorded as the breaking strength. The larger the breaking strength, the better the mechanical strength.
〔成形性〕
(1)　スウェル比
　ペレットを用いて測定した。
　キャピラリーレオメータ（（株）東洋精機製作所、キャピログラフグラフ1D）を用い、200℃、せん断速度100（1／sec）、オリフィス直径2.0mmで押し出された溶融物のストランド径をノギスで測定し、ストランド直径をオリフィス直径で除した数値を組成物のスウェル比とした。 [Moldability]
(1) Swell ratio Measured using pellets.
Using a capillary rheometer (Toyo Seiki Seisakusho Co., Ltd., Capillograph Graph 1D), measure the strand diameter of the extruded melt at 200 ° C., shear rate 100 (1 / sec), and orifice diameter 2.0 mm with a caliper. The value obtained by dividing the strand diameter by the orifice diameter was used as the swell ratio of the composition.
(2)　メルトマスフローレイト（ＭＦＲ）
　ペレットを用い、ASTM D1238に準拠して、200℃、公称荷重49Ｎの条件で測定した。 (2) Melt mass flow rate (MFR)
Measurements were made using pellets in accordance with ASTM D1238 under the conditions of 200 ° C. and a nominal load of 49 N.
〔フローマーク評価〕
　ペレットを用い、40mm/s、100mm/s、又は200mm/sの射出速度で、下記の条件で射出成形し、厚さ2mm×幅125mm×長さ125mmのプレートを作製した。各射出速度でのフローマークの有無を目視にて観察し、以下の評価基準に従って、フローマークについて評価した。 [Flow mark evaluation]
Using pellets, injection molding was performed at an injection rate of 40 mm / s, 100 mm / s, or 200 mm / s under the following conditions to prepare a plate having a thickness of 2 mm, a width of 125 mm, and a length of 125 mm. The presence or absence of the flow mark at each injection speed was visually observed, and the flow mark was evaluated according to the following evaluation criteria.
〔射出成形条件〕
射出成形機：EC100SX II-4B（東芝機械（株)製）
射出成形温度：200℃
射出圧力：120MPa　保圧30MPa
射出時間：2sec
金型温度：40℃ [Injection molding conditions]
Injection molding machine: EC100SX II-4B (manufactured by Toshiba Machine Co., Ltd.)
Injection molding temperature: 200 ° C
Injection pressure: 120MPa Holding pressure 30MPa
Injection time: 2sec
Mold temperature: 40 ℃
〔評価基準〕
◎：射出速度40mm/sで、フローマークの発生無し。
○：射出速度40mm/sでは、フローマークが発生するが、射出速度100mm/sでは、フローマークの発生無し。
△：射出速度100mm/sでは、フローマークが発生するが、射出速度200mm/sでは、フローマークの発生無し。
×：射出速度200mm/sで、フローマーク発生。 〔Evaluation criteria〕
⊚: Injection speed 40 mm / s, no flow mark.
◯: A flow mark is generated at an injection speed of 40 mm / s, but no flow mark is generated at an injection speed of 100 mm / s.
Δ: Flow marks are generated at an injection speed of 100 mm / s, but no flow marks are generated at an injection speed of 200 mm / s.
×: Flow mark occurs at injection speed of 200 mm / s.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　以上の結果より、実施例１～１１の熱可塑性エラストマー組成物は、比較例２、３及び５～９と対比して、フローマークの発生を最小限にすることができ、射出成形による成形材料としても有用であることが分かる。なかでも、実施例１、９、１０の対比から、ＭＦＲの大きいプロピレン単独重合体Ｄをプロピレン単独重合体Ｂよりも少ない量で配合することにより、フローマークがより効果的に改善されることが分かる。
　また、比較例１では、フローマークは問題ないものの、ＭＦＲが小さすぎるため成形性が、また比較例４では、同じくフローマークは問題ないものの、硬度が高すぎて柔軟性に欠けるため、成形性や成形品として問題が生じることが分かる。 From the above results, the thermoplastic elastomer compositions of Examples 1 to 11 can minimize the occurrence of flow marks as compared with Comparative Examples 2, 3 and 5 to 9, and are molded materials by injection molding. It turns out that it is also useful. In particular, from the comparison of Examples 1, 9 and 10, the flow mark can be improved more effectively by blending the propylene homopolymer D having a large MFR in an amount smaller than that of the propylene homopolymer B. I understand.
Further, in Comparative Example 1, although there is no problem with the flow mark, the MFR is too small, so that the moldability is good. In Comparative Example 4, although the flow mark is also not a problem, the hardness is too high and the flexibility is lacking. It can be seen that problems occur as molded products.
　本発明の熱可塑性エラストマー組成物は、自動車、電子材料、家電、電気機器、医療用具、包装資材、文具・雑貨用品等の各種成形品に用いることができ、さらには、チューブ、クッション体、フィルム、シート等の各種部材に用いられる。 The thermoplastic elastomer composition of the present invention can be used for various molded products such as automobiles, electronic materials, home appliances, electric devices, medical tools, packaging materials, stationery and miscellaneous goods, and further, tubes, cushions, films, etc. , Used for various members such as sheets.

Claims (9)

  1. 　熱可塑性スチレン系エラストマーＡとプロピレン単独重合体Ｂと軟化剤Ｃを含有し、熱可塑性スチレン系エラストマーＡ 100質量部に対して、前記プロピレン単独重合体Ｂの含有量が10～400質量部、前記軟化剤Ｃの含有量が10～300質量部であり、前記プロピレン単独重合体Ｂの重量平均分子量と数平均分子量の比（重量平均分子量／数平均分子量）が10.0～25.0、スウェル比が1.1～2.5である、熱可塑性エラストマー組成物。 The content of the propylene homopolymer B is 10 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic styrene elastomer A, which contains the thermoplastic styrene-based elastomer A, the propylene homopolymer B and the softening agent C. The content of the softener C is 10 to 300 parts by mass, the ratio of the weight average molecular weight to the number average molecular weight of the propylene homopolymer B (weight average molecular weight / number average molecular weight) is 10.0 to 25.0, and the swell ratio is 1.1 to 1.1 to The thermoplastic elastomer composition which is 2.5.
  2. 　プロピレン単独重合体Ｂの230℃、公称荷重21.2Ｎでのメルトマスフローレイトが、1～30g/10minである、請求項１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 melt mass flow rate of the propylene homopolymer B at 230 ° C. and a nominal load of 21.2 N is 1 to 30 g / 10 min.
  3. 　さらに、230℃、公称荷重21.2Ｎでのメルトマスフローレイトが100g/10min以上であるプロピレン単独重合体Ｄを、熱可塑性スチレン系エラストマーＡ100質量部に対して、3～400質量部含有し、該プロピレン単独重合体Ｄの含有量が、プロピレン単独重合体Ｂ 100質量部に対して、1～80質量部である、請求項２記載の熱可塑性エラストマー組成物。 Further, the propylene homopolymer D having a melt mass flow rate of 100 g / 10 min or more at 230 ° C. and a nominal load of 21.2 N is contained in an amount of 3 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic styrene-based elastomer A. The thermoplastic elastomer composition according to claim 2, wherein the content of the homopolymer D is 1 to 80 parts by mass with respect to 100 parts by mass of the propylene homopolymer B.
  4. 　プロピレン単独重合体Ｂのｚ平均分子量が、1,000,000～3,000,000である、請求項３記載の熱可塑性エラストマー組成物。 The thermoplastic elastomer composition according to claim 3, wherein the propylene homopolymer B has a z average molecular weight of 1,000,000 to 3,000,000.
  5. 　熱可塑性スチレン系エラストマーＡの重量平均分子量が、50,000～500,000である、請求項１～４いずれか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 4, wherein the thermoplastic styrene elastomer A has a weight average molecular weight of 50,000 to 500,000.
  6. 　熱可塑性スチレン系エラストマーＡが、制御分布型スチレン系ブロック共重合体を含有する、請求項１～５いずれか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 5, wherein the thermoplastic styrene elastomer A contains a controlled distribution type styrene block copolymer.
  7. 　軟化剤Ｃが、パラフィン系オイル及びナフテン系オイルから選択される少なくとも1種を含有する、請求項１～６いずれか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 6, wherein the softener C contains at least one selected from paraffin-based oils and naphthenic-based oils.
  8. 　熱可塑性エラストマー組成物のスウェル比が1.1～2.5である、請求項１～７いずれか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 7, wherein the swell ratio of the thermoplastic elastomer composition is 1.1 to 2.5.
  9. 　熱可塑性エラストマー組成物の200℃、公称荷重49Ｎでのメルトマスフローレイトが、6～30g/10minである、請求項１～８いずれか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 8, wherein the melt mass flow rate of the thermoplastic elastomer composition at 200 ° C. and a nominal load of 49 N is 6 to 30 g / 10 min.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0866990A (en) * 1994-06-20 1996-03-12 Mitsubishi Chem Corp Composite molded body and its manufacture
JPH09296093A (en) * 1996-05-07 1997-11-18 Mitsubishi Chem Corp Thermoplastic elastomer composition
JPH10130452A (en) * 1996-10-30 1998-05-19 Mitsubishi Chem Corp Thermoplastic elastomer composition
JP2000103934A (en) * 1998-09-29 2000-04-11 Mitsubishi Chemicals Corp Thermoplastic elastomer composition
JP2000109640A (en) * 1998-10-09 2000-04-18 Mitsubishi Chemicals Corp Thermoplastic elastomer composition
JP2003183460A (en) * 2001-12-18 2003-07-03 Grand Polymer Co Ltd Polypropylene resin composition for injection molding, polypropylene resin molded article and its manufacturing method
JP2008291117A (en) * 2007-05-24 2008-12-04 Aron Kasei Co Ltd Heat-resistant styrenic thermoplastic elastomer composition
WO2009119592A1 (en) * 2008-03-25 2009-10-01 旭化成ケミカルズ株式会社 Elastomer composition and storage cover for airbag system
JP2018070809A (en) * 2016-11-01 2018-05-10 アロン化成株式会社 Thermoplastic elastomer composition for composite molded body

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0866990A (en) * 1994-06-20 1996-03-12 Mitsubishi Chem Corp Composite molded body and its manufacture
JPH09296093A (en) * 1996-05-07 1997-11-18 Mitsubishi Chem Corp Thermoplastic elastomer composition
JPH10130452A (en) * 1996-10-30 1998-05-19 Mitsubishi Chem Corp Thermoplastic elastomer composition
JP2000103934A (en) * 1998-09-29 2000-04-11 Mitsubishi Chemicals Corp Thermoplastic elastomer composition
JP2000109640A (en) * 1998-10-09 2000-04-18 Mitsubishi Chemicals Corp Thermoplastic elastomer composition
JP2003183460A (en) * 2001-12-18 2003-07-03 Grand Polymer Co Ltd Polypropylene resin composition for injection molding, polypropylene resin molded article and its manufacturing method
JP2008291117A (en) * 2007-05-24 2008-12-04 Aron Kasei Co Ltd Heat-resistant styrenic thermoplastic elastomer composition
WO2009119592A1 (en) * 2008-03-25 2009-10-01 旭化成ケミカルズ株式会社 Elastomer composition and storage cover for airbag system
JP2018070809A (en) * 2016-11-01 2018-05-10 アロン化成株式会社 Thermoplastic elastomer composition for composite molded body

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