WO2021024347A1 - Composition d'élastomère thermoplastique - Google Patents

Composition d'élastomère thermoplastique 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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mass
molecular weight
elastomer composition
thermoplastic elastomer
styrene
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PCT/JP2019/030681
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English (en)
Japanese (ja)
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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 PCT/JP2019/030681 priority Critical patent/WO2021024347A1/fr
Priority to JP2021538562A priority patent/JP7157257B2/ja
Publication of WO2021024347A1 publication Critical patent/WO2021024347A1/fr

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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

Composition d'élastomère thermoplastique contenant un élastomère à base de styrène thermoplastique A, un homopolymère de propylène B, et un plastifiant C, la quantité contenue d"homopolymère de propylène B étant de 10 à 400 parties en masse, et la quantité contenue de plastifiant C étant de 10 à 300 parties en masse, par rapport à 100 parties en masse de l'élastomère à base de styrène thermoplastique A ; et, en ce qui concerne l'homopolymère de propylène B, le rapport (poids moléculaire moyen en poids/poids moléculaire moyen en nombre) entre le poids moléculaire moyen en poids et le poids moléculaire moyen en nombre est de 10,0 à 25,0, et le taux de gonflement est de 1,1 à 2,5. La composition élastomère thermoplastique selon la présente invention peut être utilisée pour divers produits moulés tels que des automobiles, des matériels électroniques, des appareils électroménagers, des dispositifs électriques, des instruments médicaux, des matériaux d'emballage, et des articles de papeterie/articles divers, et peut également être utilisée pour divers éléments tels que des tubes, des corps de coussin, des films et des feuilles.
PCT/JP2019/030681 2019-08-05 2019-08-05 Composition d'élastomère thermoplastique WO2021024347A1 (fr)

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PCT/JP2019/030681 WO2021024347A1 (fr) 2019-08-05 2019-08-05 Composition d'élastomère thermoplastique
JP2021538562A JP7157257B2 (ja) 2019-08-05 2019-08-05 熱可塑性エラストマー組成物

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WO2009119592A1 (fr) * 2008-03-25 2009-10-01 旭化成ケミカルズ株式会社 Composition d’élastomère et enveloppe de stockage pour système de coussin de sécurité gonflable
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JPH0866990A (ja) * 1994-06-20 1996-03-12 Mitsubishi Chem Corp 複合成形体及びその製造方法
JPH09296093A (ja) * 1996-05-07 1997-11-18 Mitsubishi Chem Corp 熱可塑性エラストマー組成物
JPH10130452A (ja) * 1996-10-30 1998-05-19 Mitsubishi Chem Corp 熱可塑性エラストマー組成物
JP2000103934A (ja) * 1998-09-29 2000-04-11 Mitsubishi Chemicals Corp 熱可塑性エラストマー組成物
JP2000109640A (ja) * 1998-10-09 2000-04-18 Mitsubishi Chemicals Corp 熱可塑性エラストマー組成物
JP2003183460A (ja) * 2001-12-18 2003-07-03 Grand Polymer Co Ltd 射出成形用ポリプロピレン樹脂組成物、ポリプロピレン樹脂成形品、およびその製造方法
JP2008291117A (ja) * 2007-05-24 2008-12-04 Aron Kasei Co Ltd 耐熱性スチレン系熱可塑性エラストマー組成物
WO2009119592A1 (fr) * 2008-03-25 2009-10-01 旭化成ケミカルズ株式会社 Composition d’élastomère et enveloppe de stockage pour système de coussin de sécurité gonflable
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