JP2018145406A - Styrenic thermoplastic elastomer composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrenic thermoplastic elastomer composition which achieves both excellent heat resistance and flexibility.SOLUTION: There are provided: a resin composition which contains (a) 100 pts.mass of a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, (b) 5-120 pts.mass of a polypropylene resin having a melt mass flow rate at 230°C under 21.18 N according to JIS K7210 of 1-10 g/10 min, and (c) 100-280 pts.mass of a rubber softener and which has a Shore A hardness according to JIS K6253 of 30-95 and a melt mass flow rate at 230°C under 21.18 N according to JIS K7210 of 13-100 g/10 min; and a molded article and a grip material comprising the resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a styrenic thermoplastic elastomer composition and use thereof.

  In recent years, thermoplastic elastomer compositions have been frequently used in the field of living materials. As the thermoplastic elastomer composition, various thermoplastic elastomer compositions such as polyolefin, polyurethane, polyester, polyamide, polystyrene, and polyvinyl chloride are used. Among these, as sealing members for food packaging containers and medical containers such as pharmaceuticals, olefins are particularly preferred from the viewpoints of economy, stability of mechanical properties, and resistance to use in a wide temperature range from room temperature to high temperature. Attention has been focused on thermoplastic elastomer compositions. However, the olefin-based thermoplastic elastomer composition has a problem that a plasticizer such as a rubber softener that is blended to impart flexibility tends to cause bleed-out.

  Patent Document 1 has a high gas barrier property and an easy-opening property, is excellent in compression deformation resistance and bleed-out resistance in any temperature environment from room temperature to high temperature, has good moldability, As a thermoplastic elastomer composition that can be suitably used as a material for packaging and medical articles, (a) a hydrogenated block copolymer (a1) of an aromatic vinyl compound and a conjugated diene compound, and an aromatic A thermoplastic elastomer resin composition comprising one or more selected from the group consisting of a block copolymer (a2) of an aromatic vinyl compound and isobutylene; (b) a polyolefin-based resin; and (c) a rubber softener Has been.

  In the examples of Patent Document 1, three types of polypropylene resins are used as the polypropylene resins at 230 ° C. and 21.18 N with a melt mass flow rate of 15 g / 10 min, 54 g / 10 min, and 0.6 g / 10 min. It has been.

JP, 2006-196601, A

  When the present inventors used an existing styrenic thermoplastic elastomer composition for injection molding, it was found that there was a problem of yellowing. As a result of studying the cause by the present inventors, it was found that the cause is that a polypropylene resin having a high melt mass flow rate decomposed with peroxide is used in order to improve fluidity. .

  Therefore, when the present inventors used a polypropylene resin having a melt mass flow rate of 1 to 10 g / 10 min at 230 ° C. and 21.18 N according to JIS K7210 as the polypropylene resin, yellowing was improved. Thus, it was found that a styrenic thermoplastic elastomer composition having both excellent heat resistance and flexibility can be obtained.

  That is, an object of the present invention is to provide a styrenic thermoplastic elastomer composition that achieves both excellent heat resistance and flexibility.

The gist of the present invention is as follows.
(1) (a) 100 mass parts of hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound, (b) Melt mass flow rate at 230 ° C. and 21.18 N in accordance with JIS K7210 is 1 to 1 It includes 5 to 120 parts by mass of a polypropylene-based resin that is 10 g / 10 min, and (c) 100 to 280 parts by mass of a softening agent for rubber. The resin composition whose melt mass flow rate in 21 degreeC and 21.18 N is 13-100 g / 10min.
(2) (a) 100 parts by mass of hydrogenated product of block copolymer of aromatic vinyl compound and conjugated diene compound, (b) Melt mass flow rate at 230 ° C. and 21.18 N in accordance with JIS K7210 is 0.00. 1 to 10 g / 10 min polypropylene resin 5 to 80 parts by mass and (c) rubber softener 201 to 280 parts by mass, Shore A hardness 30 to 45 according to JIS K6253 and JIS K7210 The resin composition whose melt mass flow rate in 230 degreeC and 21.18N was 13-100 g / 10min.
(3) The resin composition according to (1) or (2), wherein the component (a) is a styrene / ethylene / butene / styrene block copolymer (SEBS).
(4) The resin composition according to any one of (1) to (3), wherein the component (b) is a polypropylene homopolymer.
(5) A molded article comprising the resin composition according to any one of (1) to (4).
(6) A grip material comprising the resin composition according to any one of (1) to (4).

  The resin composition of the present invention has both excellent heat resistance and flexibility.

The present invention is described in detail below.
(A) Hydrogenated product of block copolymer of aromatic vinyl compound and conjugated diene compound The component (a) is a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound. When the component (a) is used, compression set characteristics and flexibility are particularly good.

  The aromatic vinyl compound is a polymerizable monomer having a polymerizable carbon-carbon double bond and an aromatic ring. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinyltoluene. . Of these, styrene is preferred. One or more of these can be used as the aromatic vinyl compound.

  The conjugated diene compound is a polymerizable monomer having a structure in which two carbon-carbon double bonds are connected by one carbon-carbon single bond. Examples of the conjugated diene compound include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and chloroprene (2-chloro-1,3-butadiene). Butadiene) and the like. Of these, 1,3-butadiene and isoprene are preferred. One or more of these can be used as the conjugated diene compound.

  The component (a) includes at least one polymer block A mainly composed of an aromatic vinyl compound, preferably 2 or more from the viewpoint of mechanical strength and moldability, and a heavy component mainly composed of a conjugated diene compound. It is a block copolymer composed of one or more combined blocks B. For example, the block copolymer which has structures, such as AB, ABA, and ABABABA, can be mentioned.

  The content of the structural unit derived from the aromatic vinyl compound of component (a) is preferably 5 to 60% by mass, more preferably 20 to 50% by mass, from the viewpoint of heat resistance.

  The polymer block A is a polymer block composed only of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound and a conjugated diene compound. When the polymer block A is a copolymer block, the content of the structural unit derived from the aromatic vinyl compound in the polymer block A is usually 51% by mass or more, preferably 70% by mass from the viewpoint of heat resistance. % Or more, more preferably 90% by mass or more. The distribution of the structural unit derived from the conjugated diene compound in the polymer block A is not particularly limited and is arbitrary. When there are two or more polymer blocks A, these may have the same structure or different structures.

  The polymer block B is a polymer block composed only of a conjugated diene compound or a copolymer block of an aromatic vinyl compound and a conjugated diene compound. In the case where the polymer block B is a copolymer block, the content of the structural unit derived from the conjugated diene compound in the polymer block B is usually 51% by mass or more, preferably 70% by mass from the viewpoint of flexibility. As mentioned above, More preferably, it is 90 mass% or more. The distribution of the structural unit derived from the aromatic vinyl compound in the polymer block is not particularly limited and is arbitrary. The bonding mode between the conjugated diene compound and the conjugated diene compound (hereinafter sometimes abbreviated as microstructure) is not particularly limited and is arbitrary. When there are two or more polymer blocks B, these may have the same structure or different structures.

  Hydrogenation rate of component (a) (carbon to carbon single bond by hydrogenation relative to the number of carbon to carbon double bonds in the block copolymer of aromatic vinyl compound and conjugated diene compound before hydrogenation) The ratio of the number of bonds is not particularly limited, but is usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more from the viewpoint of heat resistance.

  When the conjugated diene polymer block of the component (a) is a butadiene polymer block, the microstructure is preferably 20-50 mol%, more preferably 1,2-bonds from the viewpoint of flexibility. It is 25-45 mol%. In addition, from the viewpoint of heat resistance, the 1,2-bond may be selectively hydrogenated.

  When the conjugated diene polymer block of the component (a) is a copolymer block of isoprene and butadiene, the microstructure is preferably less than 50 mol% in terms of 1,2-bond, from the viewpoint of heat resistance. More preferably, it is less than 25 mol%, More preferably, it is less than 15 mol%.

  When the conjugated diene polymer block of the component (a) is an isoprene polymer block, from the viewpoint of flexibility, the microstructure has 1,4-bonds of preferably 70 to 100 mol%. The hydrogenation rate is preferably 90 mol% or more from the viewpoint of heat resistance.

  When the conjugated diene polymer block of the component (a) is an isoprene polymer block, from the viewpoint of gas barrier properties, the microstructure is such that the sum of 1,2-bonds and 3,4-bonds is 80 mol%. As mentioned above, Preferably it is 90 mol% or more, More preferably, it is 95 mol% or more. The hydrogenation rate is preferably 90 mol% or more from the viewpoint of heat resistance. Such a copolymer is often referred to as a styrene / vinyl (ethylene / propylene) / styrene copolymer (V-SEPS). The glass transition temperature of the styrene / vinyl (ethylene / propylene) / styrene copolymer (V-SEPS) is preferably −40 to 20 ° C.

  In this specification, according to JIS K7121-1987, the glass transition temperature is kept at 200 ° C. for 5 minutes using an RDC220 DSC type differential scanning calorimeter manufactured by SII, and reaches −100 ° C. at 10 ° C./min. It is the midpoint glass transition temperature calculated from the curve of the last temperature rising process measured by the program which cools, hold | maintains at -50 degreeC for 3 minutes, and heats up to 10 degreeC / min 150 degreeC.

  The number average molecular weight of the component (a) is preferably 80,000 to 1,500,000, more preferably 100,000 to 550,000, still more preferably, from the viewpoints of moldability and compression set resistance. 100,000 to 400,000. The molecular weight distribution (mass average molecular weight / number average molecular weight) is preferably 10 or less from the viewpoint of mechanical properties.

  Examples of the component (a) include a styrene / ethylene / butene block copolymer (SEB), a styrene / ethylene / propylene block copolymer (SEP), and a styrene / ethylene / butene / styrene block copolymer (SEBS). Styrene / ethylene / propylene / styrene copolymer block (SEPS), styrene / ethylene / ethylene / propylene / styrene block copolymer (SEEPS) and styrene / vinyl (ethylene / propylene) / styrene copolymer (V-SEPS) ) And the like. Among these, from the viewpoints of flexibility and compressive strain resistance under high temperature environment, styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS) and Styrene / ethylene / ethylene / propylene / styrene block copolymer (SEEPS) is preferred.

(B) Polypropylene Resin The component (b) is a polypropylene resin and functions to improve mechanical strength and stabilize moldability. Polypropylene resins are preferable to other polyolefin resins from the viewpoints of heat resistance and molding processability. Examples of polypropylene resins include propylene homopolymers, propylene and other small amounts of α-olefins (for example, ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene). And copolymers (including block copolymers and random copolymers).

  The melting enthalpy of the component (b) is preferably 60 J / g or less, more preferably 40 J / g or less, from the viewpoint of flexibility. From the viewpoint of mechanical strength, it is preferably 60 J / g or more, more preferably 80 J / g or more. From the viewpoint of heat resistance, it is preferably 100 J / g or more, more preferably 110 J / g or more. The melting point is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, from the viewpoints of heat resistance and mechanical strength. Although there is no upper limit of the melting point, it is usually about 167 ° C. because it is a crystalline propylene polymer.

  In this specification, the melting enthalpy of polypropylene resin is RDC220 type DSC type differential scanning calorimeter manufactured by SII, held at 230 ° C. for 5 minutes, cooled to −10 ° C. at 10 ° C./min, The temperature was calculated from a second melting curve (melting curve measured in the last heating process) measured by a program in which the temperature was maintained at −10 ° C. for 5 minutes and the temperature was raised to 230 ° C. at 10 ° C./min. The melting point was calculated from the peak top appearing on the highest temperature side in the second melting curve.

  The melt mass flow rate at 230 ° C. and 21.18 N in accordance with JIS K7210 of the polypropylene resin is 1 to 10 g / 10 minutes. When the melt mass flow rate exceeds 10 g / 10 min, it may turn yellow when used for injection molding, and it is impossible to achieve both excellent heat resistance and flexibility, while the melt mass flow rate is 1 g. If it is less than / 10 minutes, the fluidity of the resin composition is lowered and the injection moldability is lowered.

  When the resin composition of the present invention is applied to injection molding, the melt mass flow rate is preferably 5 to 10 g / 10 minutes.

  As the polypropylene resin of the component (b), direct polymerization which is not subjected to decomposition treatment with peroxide from the viewpoint of preventing yellowing and a resin composition having both excellent heat resistance and flexibility. It is preferable to use a product.

  The compounding amount of the component (b) is 5 parts by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the component (a) from the viewpoints of workability, heat resistance and flexibility. On the other hand, from the viewpoint of flexibility, it is 120 parts by mass or less, preferably 115 parts by mass or less.

(C) Rubber softener The component (c) is a rubber softener and functions to increase flexibility. Examples of the component (c) include non-aromatic rubber softeners, aromatic rubber softeners and ester plasticizers. Among these, non-aromatic rubber softeners are preferable from the viewpoint of compatibility.

  The non-aromatic rubber softener is a non-aromatic mineral oil (hydrocarbon compound derived from petroleum or the like) or a synthetic oil (synthetic hydrocarbon compound), and is usually liquid, gel or gum at normal temperature. It is. Here, the non-aromatic system means that the mineral oil is not classified into the aromatic system in the following classification (the aromatic carbon number is less than 30%). For synthetic oils, it means that no aromatic monomer is used.

  Mineral oil used as a rubber softener is a mixture of one or more of paraffin chains, naphthene rings, and aromatic rings, and those having 30 to 45% naphthenic ring carbon number are naphthenic, aromatic Those whose group carbon number is 30% or more are called aromatic, and those that do not belong to naphthenic or aromatic group and whose paraffin chain carbon number occupies 50% or more of the total carbon number are called paraffinic Are distinguished.

  Examples of the non-aromatic rubber softener include paraffinic mineral oils such as linear saturated hydrocarbons, branched saturated hydrocarbons and derivatives thereof; naphthenic mineral oils; hydrogenated polyisobutylene, polyisobutylene, and the like. And synthetic oils such as polybutene.

  The dynamic viscosity at 37.8 ° C. of the non-aromatic rubber softener is preferably 20 to 50,000 cSt, more preferably 20 to 1,000 cSt from the viewpoint of moldability. The dynamic viscosity at 100 ° C. is preferably 5 to 1,500 cSt, more preferably 5 to 500 cSt, from the viewpoint of bleed-out resistance and heat resistance. The pour point is preferably −10 to −25 ° C. from the viewpoint of handleability during production of the composition. The flash point (COC) is preferably 170 to 350 ° C. from the viewpoint of safety. The mass average molecular weight is preferably 100 to 2,000 from the viewpoint of bleed-out resistance.

  Commercial examples of the non-aromatic rubber softener include isoparaffin hydrocarbon oil “NA Solvent (trade name)” manufactured by Nippon Oil & Fats Co., Ltd., n-paraffin process oil “Diana Process Oil PW” manufactured by Idemitsu Kosan Co., Ltd. -90 (trade name) ”and“ Diana Process Oil PW-380 (trade name) ”, synthetic isoparaffinic hydrocarbon“ IP-solvent 2835 (trade name) ”from Idemitsu Petrochemical Co., Ltd. and n of Sanko Chemical Industry Co., Ltd. -Paraffinic process oil "Neothiozole (trade name)" and the like can be mentioned. Among these, paraffinic mineral oil is preferable from the viewpoint of compatibility, and paraffinic mineral oil having a small number of aromatic carbon atoms is more preferable. One or more of these can be used as the component (c).

  The compounding amount of the component (c) is 280 parts by mass or less, preferably 250 parts by mass or less with respect to 100 parts by mass of the component (a) from the viewpoint of bleed resistance. On the other hand, the lower limit of the amount of the component (c) is 100 parts by mass or more, preferably 120 parts by mass or more, from the viewpoint of obtaining a flexibility improving effect.

(D) Physical properties of the resin composition of the present invention The resin composition of the present invention has a shore A hardness of 30 to 95 based on JIS K6253 and a melt mass flow rate at 230 ° C. of 21.18 N based on JIS K7210. 13 to 100 g / 10 min.

If the hardness is less than 30, the molded product has a sticky feeling and is not suitable as a grip material. On the other hand, if the hardness exceeds 95, the molded product is hard, and the tactile sensation is lowered, so that it is not suitable as a grip material.
The hardness is preferably 35 to 75.

  When the melt mass flow rate is less than 13 g / 10 minutes, the injection moldability is lowered due to low fluidity. On the other hand, when the melt mass flow rate exceeds 100 g / 10 minutes, the fluidity is too high, and the tensile strength, Mechanical properties such as compression set are reduced.

(E) Other components Other resins or polymers and / or additives for resins can be optionally added to the resin composition of the present invention within a range that does not impair the effects of the present invention, depending on the application. . Examples of such additives for resins include pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and weathering stability. Agent, heat stabilizer, anti-slip agent, anti-blocking agent, foaming agent, crystallization aid, anti-fogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, co-crosslinking agent , Crosslinking aids, adhesives, softeners, processing aids, and the like. These additives can be used singly or in appropriate combination of two or more.

  Other resins or polymers to be added include unmodified polyolefin, polystyrene, acrylic resin, polyphenylene sulfide resin, polyether ether ketone resin, polyester resin, polysulfone, polycarbonate, polyacetal, polyphenylene ether, polyimide, polyetherimide, acrylonitrile, Examples thereof include butadiene / styrene copolymer (ABS), conjugated diene rubber, styrene rubber, phenol resin, melamine resin, silicone resin, and epoxy resin. The addition amount of these resins or polymers is preferably 0.1 to 30% by mass with respect to the total mass of the resin composition.

  Examples of the pigment include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake, thioindigo, phthalocyanine, anthraquinone, etc.). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5% by mass or less, preferably 0.1 to 3% by mass in total with respect to the total mass of the resin composition.

  Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide (Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium carbonate, barium carbonate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.

  Examples of the lubricant include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

  Plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dicarboxylic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), polyethylene wax, lubricating oil, and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

  Antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.) , Phosphorus-based (tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonate etc.), amine-based (N, N′-diisopropyl-p-phenylenediamine etc.) antioxidant Agents.

  Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate esters such as higher alcohol phosphate esters. Salts such as Examples of the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.

  Examples of the antistatic agent include the aforementioned surfactants, fatty acid esters, and polymer type antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  The addition amount of various additives such as the filler, lubricant, plasticizer, mold release agent, antioxidant, flame retardant, ultraviolet absorber, antibacterial agent, surfactant, antistatic agent and the like detracts from the object of the present invention. Although it does not specifically limit according to a use within the range which is not, It is preferable that it is 0.1-30 mass%, respectively with respect to the total mass of a resin composition.

(F) Manufacturing method of resin composition For example, the cylinder temperature of the part which knead | mixes with a kneader is 100-300 degreeC normally, Preferably it is 150-250 degreeC. The kneading time is usually 0.1 to 30 minutes, preferably 0.5 to 5 minutes.

(G) Molded product comprising resin composition Various molded products comprising the resin composition of the present invention include extruded sheets, films, injection molded products, inflation molded products, blow molded products, hollow molded products, compression molded products, and calendars. A molded body etc. are mentioned.

(1) Extruded sheet, extruded film An extruded film or an extruded sheet can be obtained by molding the resin composition of the present invention with a general T-die extruder. Specifically, it is molded by a single-screw extruder at a predetermined cylinder temperature of usually 180 to 250 ° C. and a predetermined cast roll temperature of usually 0 to 70 ° C. to form an extruded film or sheet.

(2) Injection-molded product The resin composition of the present invention melts and softens pellets and fills the mold, and an injection-molded product is obtained at a molding temperature of usually 180 to 250 ° C. and a molding cycle of usually 20 to 120 seconds.

(3) Inflation molded body Specifically, an inflation molded body made of the resin composition of the present invention is an upward direction opposite to the direction of gravity from the inflation die at a predetermined cylinder temperature in a single-screw extruder. The film can be extruded and blown to obtain an blown film.

  The blow-up rate of the inflation film is usually 0.5 to 10, preferably 1 to 5, and the take-up speed is usually 1 to 40 m / min, preferably 2 to 30 m / min, more preferably 4 to 30 m / min. is there. Although the thickness of a film is not specifically limited, Usually, it is 10-300 micrometers.

  The blown film made of the resin composition of the present invention may be subjected to laminated blow molding which is extruded simultaneously with other thermoplastic resins.

(4) Blow molding (injection blow molding, stretch blow molding, direct blow molding)
For example, in injection blow molding, a pellet is obtained by melting pellets of the resin composition of the present invention with a general injection blow molding machine and filling a mold. After the obtained preform is reheated in an oven (heating furnace), it is placed in a mold maintained at a constant temperature, and a blow bottle can be formed by sending and blowing pressurized air. .

(H) Use of resin composition The resin composition of the present invention can be molded by the various molding methods described above, and is not particularly limited to automobile parts, electrical / electronic parts, life-related products, industrial materials. It can be used for various purposes such as agricultural materials, medical or hygiene products.

  Auto parts include tubes, quick connectors, air brakes, CVJ boots, suspension boots, rack and pinion boots, steering rod covers, AT slid covers, leaf spring bushes, ball joint retainers, lever stab plates, door latch strikers, seats Belt parts, silencer gear, control cable cover, switch, side trim molding, emblem, weather strip, ceiling material, interior seat, bumper molding, side molding, air spoiler, air duct hose, cup holder, side brake grip, shift knob cover, seat Adjustment knob, flapper door seal, wire harness grommet, suspension cover boot, glass guide, inner belt line sea , Roof guide, trunk lid seal, molded quarter window gasket, corner molding, glass encapsulation, hood seal, glass run channel, secondary seal, various packings, bumper parts, body panel, side shield, instrument panel skin, Examples include mechanical parts such as door skins, hoses, steering wheels, wire harness covers, and seat adjuster covers, interior parts, and exterior parts.

  Examples of electrical / electronic products include tubes, silencer gears, earphone covers, connector covers, remote control keypads, camera grips, and wire covering materials.

  As life-related products, sports shoes soles, ski boots, tennis rackets, ski bindings, sports equipment such as bat grips, pen grips, toothbrush grips, hair brushes, fashion belts, various caps, miscellaneous goods such as shoe inner soles, etc. Is mentioned.

  Industrial materials include hydraulic hoses, pneumatic hoses, railroad pads, conveyor belts, hoses, seals and packing, gaskets for building materials, waterproof sheets, etc. In addition, infusion bags, medical containers, beverage bottles, etc. It can be used for various purposes.

  The resin composition of the present invention has both excellent heat resistance and flexibility, and since it does not turn yellow even when used for injection molding, a tool, a golf component, obtained by injection molding, It is suitable as a grip material for bicycle parts, automobile parts, electrical / electronic products, daily life-related products, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

(Examples 1-6 and Comparative Examples 1-4)
A compound having a compounding ratio (parts by mass) shown in any one of Table 1 (Examples) and Table 2 (Comparative Examples) was converted into a twin-screw extruder (manufactured by Technobell, KZW-15, screw diameter 15 mm, L / L). D = 30, die outlet temperature 200 ° C., rotation speed 200 rpm), and melt kneading, and a pellet of a thermoplastic elastomer resin composition was obtained by a strand cut method. Thereafter, using a hydraulic 100-ton automatic heating press manufactured by Shoji Co., Ltd., the press temperature was set to 190 ° C., and the sheet was formed at a pressure of 10 MPa. After preheating was pressurized for 6 minutes at 10 MPa for 6 minutes, using a cooling press set at 25 ° C., it was compressed at 10 MPa and cooled for 5 minutes (chiller cooling temperature set at 25 ° C.) to prepare a measurement sample. The samples prepared by the above methods were used for various physical property evaluation tests. Various physical property measurement results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
In the following examples and comparative examples, various analysis methods were performed according to the following procedures.

(Melt mass flow rate: MFR)
The melt mass flow rate at 230 ° C. and 21.18 N was measured according to JIS K7210.

(hardness)
In accordance with JIS K6253 (hardness test method), Shore A (instantaneous value) and Shore D (value after 5 seconds) hardness were determined using a dilometer.

(Tensile strength test)
The resin compositions obtained in the examples and comparative examples were subjected to a tensile test according to JIS K6301 (distance between marked lines 20 mm), tensile speed 500 mm / min, 23 ° C., tensile elongation at break (%), tensile The breaking strength (MPa) was determined.

(Compression set test 1)
In accordance with JIS K6262, in a 23 ° C. atmosphere, the compression amount was 25% and held for 24 hours, and then the permanent strain amount (%) after release was determined.

(Compression set test 2)
In accordance with JIS K6262, in a 70 ° C. atmosphere, the compression amount was 25% and held for 24 hours, and then the permanent strain amount (%) after release was determined.

(Heat-resistant aging color difference test)
In accordance with JIS K7373, a color difference test was performed by a reflection measurement method to determine the yellowing degree (YI). With the blank measurement at 23 ° C. as the initial stage, samples after standing for 168 hours in a 100 ° C. atmosphere and after standing for 168 hours in a 120 ° C. atmosphere were measured to determine the yellowing degree (YI).

(Crystallization speed)
The measurement is an isothermal crystallization measurement method, and the measuring device is DSC7 (manufactured by PerkinElmer). The sample temperature is 320 ° C / min in a nitrogen atmosphere, the sample shape is pellets, and the temperature is increased to 230 ° C. After holding for 5 minutes, the temperature was lowered to a measurement temperature of 115 ° C. and the temperature was maintained. From the measured DSC curve, the time from the rise of the exothermic peak due to crystallization after temperature holding to ½ of the peak area was calculated, and the value was taken as the crystallization rate (seconds).

The raw materials used are shown below.
Component (a): Styrene / ethylene / butene / styrene block copolymer having a styrene content of 33% by mass, a mass average molecular weight of 265,000, a number average molecular weight of 236,000, a molecular weight distribution of 1.12 and a hydrogen conversion rate of 99% or more. .
Component (b1): Polypropylene resin not subjected to a decomposition treatment with a peroxide having a melting enthalpy of 111 J / g, a melting point of 162 ° C., and a melt mass flow rate (230 ° C., 21.18 N) of 9.0 g / 10 minutes.
Component (b2): Polypropylene resin subjected to decomposition treatment with a peroxide having a melting enthalpy of 105 J / g, a melting point of 158 ° C., and a melt mass flow rate (230 ° C., 21.18 N) of 59.0 g / 10 minutes.
Component (b3): Polypropylene resin not subjected to a decomposition treatment with a peroxide having a melting enthalpy of 76 J / g, a melting point of 140 ° C., and a melt mass flow rate (230 ° C., 21.18 N) of 0.5 g / 10 minutes.
Component (c): Idemitsu Kosan Co., Ltd., n-paraffinic process oil “Diana Process Oil PW-380 (trade name)”. Mw750, Mn652, Mw / Mn 1.15, kinematic viscosity at 40 ° C 381.6 cSt, flash point 300 ° C.
Ingredient 1 (lubricant): “Armoslip CP (trade name)” manufactured by Lion Corporation
Component 2 (weather resistance stabilizer): “Tinuvin (registered trademark) 326FL” manufactured by BASF
Component 3 (weather resistance stabilizer): “Tinuvin (registered trademark) 770” manufactured by BASF
Component 4 (antioxidant): “IRGAFOS (registered trademark) 168” manufactured by BASF
Component 5 (Antioxidant): “IRGANOX (registered trademark) 1010” manufactured by BASF

Claims (6)

  (A) 100 mass parts of hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound, (b) Melt mass flow rate at 230 ° C. and 21.18 N in accordance with JIS K7210 is 1 to 10 g / 10 5 to 120 parts by mass of a polypropylene-based resin and (c) 100 to 280 parts by mass of a rubber softener, and a Shore A hardness of 30 to 95 according to JIS K6253 and 230 ° C. according to JIS K7210, 21 A resin composition having a melt mass flow rate at 18 N of 13 to 100 g / 10 min.   (A) 100 parts by mass of a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound, (b) 0.1 to 10 g of a melt mass flow rate at 230 ° C. and 21.18 N in accordance with JIS K7210 / 10 minutes, polypropylene resin 5-80 parts by weight and (c) rubber softener 201-280 parts by weight, Shore A hardness 30-45 according to JIS K6253, and 230 ° C. according to JIS K7210 The resin composition whose melt mass flow rate in 21.18N is 13-100 g / 10min.   The resin composition according to claim 1 or 2, wherein the component (a) is a styrene / ethylene / butene / styrene block copolymer (SEBS).   The resin composition according to any one of claims 1 to 3, wherein the component (b) is a polypropylene homopolymer.   The molded object which consists of a resin composition of any one of Claims 1-4.   The grip material which consists of a resin composition of any one of Claims 1-4.