WO2015115346A1 - Thermoplastic polymer composition having excellent gas barrier properties - Google Patents

Thermoplastic polymer composition having excellent gas barrier properties Download PDF

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Publication number
WO2015115346A1
WO2015115346A1 PCT/JP2015/051952 JP2015051952W WO2015115346A1 WO 2015115346 A1 WO2015115346 A1 WO 2015115346A1 JP 2015051952 W JP2015051952 W JP 2015051952W WO 2015115346 A1 WO2015115346 A1 WO 2015115346A1
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polymer
parts
mass
block copolymer
thermoplastic polymer
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PCT/JP2015/051952
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French (fr)
Japanese (ja)
Inventor
伸浩 三輪
高山　治幸
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クラレプラスチックス株式会社
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Priority to JP2015559920A priority Critical patent/JP6589180B2/en
Publication of WO2015115346A1 publication Critical patent/WO2015115346A1/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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a thermoplastic polymer composition excellent in gas barrier properties, and a packing material, a medical member, a tube, and a hose using the thermoplastic polymer composition.
  • thermoplastic polymer compositions do not require a vulcanization process and can be molded in the same way as thermoplastic resins, so automobile parts, home appliance parts, toys, sports equipment, medical supplies, daily necessities, miscellaneous goods, etc. Is used in a wide range of fields.
  • thermoplastic polymer compositions isobutylene-based polymers having an alkenyl group at the terminal are used for a wide range of applications by utilizing excellent gas barrier properties and heat resistance.
  • thermoplastic polymer compositions using hydrogenated block copolymers of vinyl aromatic compounds and conjugated diene compounds have various properties that utilize flexibility, rubber elasticity, excellent oil retention, and excellent mechanical strength. Used for various purposes.
  • Patent Documents 1 and 2 disclose thermoplastic polymer compositions containing an isobutylene polymer, a polyolefin polymer, and a softening agent.
  • the thermoplastic polymer composition described in Patent Document 1 is not satisfactory in terms of mechanical properties such as tensile strength and surface properties, and further improvement is desired.
  • the thermoplastic polymer composition described in Patent Document 2 is not satisfactory because it does not describe mechanical properties such as gas barrier properties, surface characteristics, and tensile strength.
  • An object of the present invention is to provide a thermoplastic polymer composition excellent in mechanical properties such as gas barrier properties, fluidity, heat resistance, surface properties, and tensile strength, and a packing material, a medical member, and a tube using the thermoplastic polymer composition And to provide a hose.
  • the block copolymer obtained by hydrogenating the block copolymer mainly composed of a specific conjugated diene, and the polybutene and the propylene polymer are blended at a specific ratio, and the above-mentioned problems can be solved.
  • the present invention provides an isobutylene-based crosslinked polymer (a) obtained by crosslinking an isobutylene-based polymer having an alkenyl group at a terminal: 100 parts by mass,
  • a block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene is obtained by hydrogenation, and has a weight average molecular weight of 150,000 to 500,000.
  • Hydrogenated block copolymer (b) 10 to 100 parts by mass A hydrogenated hydrogen block having a weight average molecular weight of 200,000 to 500,000, obtained by hydrogenating a polymer block mainly composed of a vinyl aromatic compound and a block copolymer composed mainly of a conjugated diene composed of isoprene.
  • the present invention also includes a packing material, a medical member, a tube, and a hose using the thermoplastic polymer composition.
  • thermoplastic polymer composition having good physical properties such as gas barrier properties, good fluidity, heat resistance, surface properties, and tensile strength can be provided.
  • the thermoplastic polymer composition of the present invention comprises a block copolymer comprising an isobutylene-based crosslinked polymer (a), a polymer block mainly composed of a vinyl aromatic compound, and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene.
  • Hydrogenated block copolymer (b) obtained by hydrogenating a polymer, block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene
  • hydrogenated block copolymer (c) obtained by hydrogenation, polybutene (d), and propylene polymer (e).
  • the isobutylene-based crosslinked polymer (a) constituting the thermoplastic polymer composition of the present invention can be obtained by crosslinking an isobutylene-based polymer having an alkenyl group at the terminal.
  • the isobutylene polymer having an alkenyl group at the terminal is a polymer comprising an isobutylene block and having an alkenyl group at the terminal.
  • the content of isobutylene units in the isobutylene polymer is preferably 70% by weight or more, and more preferably 90% by weight or more. When the content of the isobutylene unit is within this range, the gas barrier property of the thermoplastic polymer composition of the present invention is further improved.
  • isobutylene In addition to isobutylene, other monomers may be copolymerized with the isobutylene polymer as long as the effects of the present invention are not impaired.
  • the other monomer include cationic polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.
  • the alkenyl group can be used without any limitation as long as it is a group having a carbon-carbon double bond. Specific examples include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • the isobutylene-based crosslinked polymer obtained by crosslinking an isobutylene-based polymer having an alkenyl group at the terminal is preferably crosslinked in a state where the polybutene and the polyolefin-based polymer are included.
  • Polybutene is added for the purpose of imparting flexibility and moldability.
  • the polyolefin polymer is added for the purpose of imparting fluidity.
  • Examples of the polyolefin polymer include a propylene polymer and an ethylene polymer.
  • the propylene polymer for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used.
  • ethylene polymer examples include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc.
  • An ethylene / ⁇ -olefin copolymer or the like can be used.
  • the cross-linking method may be a method using a cross-linking agent and / or a cross-linking aid, and as the cross-linking agent, a method using a peroxide or a hydrosilyl group-containing compound. A method is mentioned. From the viewpoint of increasing the crosslinking density, a method using a hydrosilyl group-containing compound is most preferable.
  • thermoplastic polymer composition of the present invention is not limited in the case where the desired utility is obtained, the polybutylene and the polyolefin polymer are further mixed with the isobutylene polymer having an alkenyl group at the terminal, and further crosslinked. It is preferable from the viewpoint of productivity and quality uniformity of the obtained thermoplastic polymer composition that the so-called dynamic crosslinking in which crosslinking is performed while adding an agent or a crosslinking aid and mixing is preferable. . More specifically, a preferred example is that an isobutylene-based crosslinked polymer is obtained by performing crosslinking at the time of melt kneading using a twin-screw extruder.
  • the hydrogenated block copolymer (b) is a block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) composed of a conjugated diene compound composed of isoprene and butadiene. It is obtained by hydrogenating the coalescence.
  • Examples of the vinyl aromatic compound constituting the polymer block (A) include styrene, ⁇ -methylstyrene, o, m or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. . Of these, styrene and ⁇ -methylstyrene are preferred.
  • a vinyl aromatic compound may be used individually by 1 type, and may use 2 or more types together.
  • the content of the vinyl aromatic compound in the hydrogenated block copolymer (b) is preferably 5 to 75% by mass, and more preferably 5 to 50% by mass. When the content of the vinyl aromatic compound is within this range, the rubber elasticity of the thermoplastic polymer composition of the present invention is further improved.
  • conjugated diene compound constituting the polymer block (B) examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned.
  • the conjugated diene compound is most preferably a mixture of isoprene and 1,3-butadiene from the viewpoint of mechanical properties such as gas barrier properties and tensile strength, and surface properties.
  • 50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (b) are preferably hydrogenated, and more preferably 75% or more are hydrogenated. It is particularly preferable that 95% or more is hydrogenated.
  • the hydrogenated block copolymer (b) may contain at least one polymer block (A) and polymer block (B), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable to contain 2 or more combined blocks (A) and 1 or more polymer blocks (B).
  • the bonding mode of the polymer block (A) and the polymer block (B) may be linear, branched, or any combination thereof.
  • the polymer block (A) is A
  • a triblock structure represented by ABA is particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
  • the weight average molecular weight of the block copolymer (b) is in the range of 150,000 to 500,000 from the viewpoint of molding processability and heat resistance, and is preferably in the range of 150,000 to 400,000.
  • the weight average molecular weight as used in this specification means the weight average molecular weight of polystyrene conversion calculated
  • Measurement condition GPC; LC Solution (manufactured by SHIMADZU) Detector: differential refractometer RID-10A (manufactured by SHIMADZU) Column: TSKgel G4000Hxl in series (made by TOSOH) Guard column: TSK guard column Hxl-L (manufactured by TOSOH) Solvent: Tetrahydrofuran Temperature: 40 ° C Flow rate: 1 ml / min Concentration: 2 mg / ml
  • the blended amount of the hydrogenated block copolymer (b) is such that the isobutylene crosslinked polymer (a) obtained by crosslinking an isobutylene polymer having an alkenyl group at the terminal is 100 masses. 10 to 100 parts by weight, and preferably 10 to 80 parts by weight with respect to the part. If the amount is less than 10 parts by mass, not only the fluidity is inferior and the moldability becomes difficult, but even if a molded product is obtained, the surface property becomes sticky and the surface property becomes extremely inferior. On the other hand, when it exceeds 100 mass parts, gas barrier property will fall.
  • Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer consisting of a polymer block mainly composed of vinyl aromatic compound and a polymer block mainly composed of conjugated diene composed of isoprene>
  • Hydrogenated block copolymer (c) is a hydrogenated block copolymer containing a polymer block (C) made of a vinyl aromatic compound and a polymer block (D) made of a conjugated diene compound made of isoprene. Is obtained.
  • Examples of the vinyl aromatic compound constituting the polymer block (C) include styrene, ⁇ -methylstyrene, o, m or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. . Of these, styrene and ⁇ -methylstyrene are preferred.
  • a vinyl aromatic compound may be used individually by 1 type, and may use 2 or more types together. Further, it may be the same as or different from the vinyl aromatic compound constituting the polymer block (A).
  • the content of the vinyl aromatic compound in the hydrogenated block copolymer (c) is preferably 5 to 75% by mass, and more preferably 5 to 50% by mass. When the content of the vinyl aromatic compound is within this range, the rubber elasticity of the thermoplastic polymer composition of the present invention is further improved.
  • conjugated diene compound in the hydrogenated block copolymer (c) examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Is mentioned.
  • a conjugated diene compound may be used individually by 1 type, and may use 2 or more types together. Among these, it is more preferable to use isoprene as the conjugated diene compound from the viewpoints of mechanical properties such as gas barrier properties and tensile strength, and surface properties.
  • 50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (c) are preferably hydrogenated, and more preferably 75% or more are hydrogenated. It is particularly preferable that 95% or more is hydrogenated.
  • the hydrogenated block copolymer (c) only needs to contain at least one polymer block (C) and one polymer block (D), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable that two or more united blocks (C) and one or more polymer blocks (D) are contained.
  • the bonding mode of the polymer block (C) and the polymer block (D) may be linear, branched, or any combination thereof.
  • the polymer block (C) is C, the polymer block ( When D) is represented by D, a triblock structure represented by CDC, or (CD) n , (CD) n -C, where n represents an integer of 2 or more Among them, those having a triblock structure represented by C—D—C are particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
  • the weight average molecular weight of the block copolymer (c) is important in the range of 200,000 to 500,000 from the viewpoint of molding processability and heat resistance, and preferably in the range of 200,000 to 400,000.
  • the blending amount of the block copolymer (c) is 100 parts by mass of the isobutylene crosslinked polymer (a) obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal.
  • the amount is 10 to 100 parts by weight, preferably 10 to 80 parts by weight.
  • the block copolymer (c) is less than 10 parts by mass, the fluidity is inferior, and when the block copolymer (c) exceeds 100 parts by mass, the gas barrier property is lowered.
  • the sum of the masses of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal. It is preferably 20 to 160 parts by mass, more preferably 20 to 120 parts by mass, and most preferably 20 to 100 parts by mass with respect to 100 parts by mass of the isobutylene-based crosslinked polymer (a). preferable.
  • the mass ratio of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is preferably in the range of 90/10 to 10/90.
  • the polybutene (d) is preferably one having a kinematic viscosity measured at 100 ° C. of 100 mm 2 / s or more from the viewpoint of gas barrier properties and surface properties of the thermoplastic polymer composition obtained, and 150 mm 2 / s or more. Some are more preferred. If the kinematic viscosity is 100 mm 2 / s or more, when the thermoplastic polymer composition of the present invention is processed into a molded product, the oil bleed is extremely reduced, and the thermoplastic polymer composition particularly excellent in gas barrier properties. Is obtained. In addition, kinematic viscosity as used in this specification is the value measured according to ASTM D445.
  • the amount of polybutene (d) is based on 100 parts by mass of the isobutylene crosslinked polymer (a) obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal.
  • the amount is 5 to 100 parts by mass, preferably 10 to 80 parts by mass. If the polybutene is less than 5 parts by mass, the fluidity is inferior, and if it exceeds 100 parts by mass, the mechanical properties such as surface properties and tensile strength are lowered.
  • propylene polymer (e) for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene or the like can be used. Among these, homopolypropylene, random polypropylene, and block polypropylene are preferably used. These propylene polymers may be used alone or in combination of two or more.
  • the melt flow rate (MFR) measured under conditions of 230 ° C. and 21 N of the propylene polymer (e) is preferably 5 g / 10 min or more. If the MFR is less than 5 g / 10 min, the fluidity of the resulting thermoplastic polymer composition is undesirably lowered.
  • the MFR can be measured according to JIS K7210.
  • the amount of the propylene-based polymer (e) is such that the isobutylene-based crosslinked polymer (a) 100 obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal is used.
  • the amount is 1 to 100 parts by weight, preferably 1 to 80 parts by weight with respect to the parts by weight.
  • the propylene polymer (e) is less than 1 part by mass, the fluidity is inferior, and when it exceeds 100 parts by mass, the flexibility is lowered.
  • thermoplastic polymer composition of the present invention includes various anti-blocking agents, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, depending on applications. It is also possible to contain a foaming agent, a colorant and the like.
  • antioxidant for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 Bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro-5,5 -Phenol antioxidants such as undecane, phosphite antioxidants, thioether antioxidants, etc.
  • the antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the above components (a) to (e) contained in the thermoplastic polymer composition of the present invention. More preferred is 0.05 to 1.0 part by mass.
  • thermoplastic polymer composition of the present invention As a method for producing the thermoplastic polymer composition of the present invention, a method used for producing a normal resin composition or a rubber composition can be employed, and a single screw extruder, twin screw extruder, Banbury mixer, heating It can manufacture by mixing each component uniformly using melt kneaders, such as a roll and various kneaders.
  • the set temperature of the processing machine can be arbitrarily selected from 150 ° C to 300 ° C.
  • thermoplastic polymer composition of the present invention may be formed into various sheet forming methods such as extrusion, injection molding, hollow molding, compression molding, calendar molding, and the like using a known method such as sheet, film, and tube. It can be formed into a molded body having an arbitrary shape.
  • thermoplastic polymer composition of the present invention can also be made into a composite molded body obtained by combining with other materials such as plastic and fabric by two-color molding method, insert molding method, co-extrusion and the like. .
  • the packing material made of the thermoplastic polymer composition of the present invention requires gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and all other fields. It can be suitably used as a packing material used for the part.
  • gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and all other fields. It can be suitably used as a packing material used for the part.
  • electric double layer capacitors are used in all devices such as automobiles, electric appliances, and electronic products.
  • the electric double layer is formed by using the packing material of the present invention as a seal for sealing an electrolyte and insulating a conductive material. Capacitors have a good gas barrier property, are less likely to cause leakage and volatilization of the electrolyte solution outside the capacitor, and have an excellent service life of the electric double layer capacitor.
  • the packing material of the present invention when used for a food container, oxygen gas in the atmosphere is less likely to permeate into the food container or flavor components in the food in the container are less likely to escape from the container. It is also excellent as a packing for use.
  • the medical member comprising the thermoplastic polymer composition of the present invention can be suitably used as a medical member that requires gas barrier properties such as water tightness and air tightness in the medical field.
  • gas barrier properties such as water tightness and air tightness in the medical field.
  • it can be used for medical infusion rubber stoppers, stoppers and rubber stoppers such as vacuum blood collection tubes, medical infusion bags, medical syringe gaskets, and prefilled syringe gaskets.
  • the medical member of the present invention has excellent gas barrier properties, and reduces atmospheric oxygen gas permeating into the member and reducing volatile components in the contents filled inside the member from volatilizing outside the member. And has the characteristics of excellent long-term storage of the contents.
  • the hose or tube made of the thermoplastic polymer composition of the present invention requires gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and other fields. It can be used as a hose or tube used in various parts.
  • gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and other fields. It can be used as a hose or tube used in various parts.
  • gas barrier property is good, viscosity increase due to evaporation of ink in the tube to the outside of the tube, It is possible to prevent problems such as the generation of bubbles derived from gas components that have permeated from the outside of the tube and hindering the supply of ink.
  • thermoplastic polymer composition of the present invention can be used as various industrial products and industrial parts regardless of the above-mentioned uses.
  • automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, and airbag covers
  • automotive exterior parts such as malls
  • Home appliance parts such as TVs, stereos, vacuum cleaners
  • underwater products such as underwater glasses and underwater camera covers
  • automotive functional parts such as rack and pinion boots, suspension boots, and constant velocity joint boots
  • Parts; use for footwear such as sports shoes and fashion sandals; belts; sports equipment; building materials such as doors and window frames; various joints; valve parts;
  • thermoplastic polymer compositions obtained in the examples and comparative examples were injection molded at 230 ° C. to obtain a sheet shape having a thickness of 2 mm, and the JIS-A hardness was measured in accordance with JIS K 6253. .
  • MFR Using the thermoplastic polymer compositions obtained in Examples and Comparative Examples, MFR (g / 10 min) under 230 ° C. and 49 N load conditions was measured according to JIS K 7210, and used as an index of fluidity. .
  • Breaking strength, breaking elongation The thermoplastic polymer compositions obtained in the examples and comparative examples were injection molded at 230 ° C. to obtain a sheet shape having a thickness of 2 mm.
  • thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to form a sheet shape having a thickness of 2 mm. From this sheet, a test piece for measuring compression set having a diameter of 29.0 mm and a thickness of 12.5 mm was prepared and allowed to stand for 24 hours under a condition of 120 ° C. and 25% compression deformation according to JIS K 6262.
  • thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to form a sheet shape having a thickness of 1 mm.
  • the gas permeability was measured from this sheet under the conditions of 23 ° C. and test gas: oxygen in accordance with JIS K 7126-1, differential pressure method.
  • test gas oxygen in accordance with JIS K 7126-1, differential pressure method.
  • a moisture permeability test method cup method for moisture-proof packaging materials, moisture permeability was measured from this sheet under conditions of 40 ° C. and relative humidity 90%, and used as an index of gas barrier properties.
  • the isobutylene-based cross-linked polymer (a) obtained by cross-linking an isobutylene-based polymer having an alkenyl group at the terminal, a polymer block mainly composed of a vinyl aromatic compound, isoprene, and butadiene as defined in the present invention.
  • a hydrogenated block copolymer (b) having a specific weight average molecular weight obtained by hydrogenation of a block copolymer comprising a polymer block mainly comprising a conjugated diene comprising a vinyl aromatic compound.
  • Hydrogenated block copolymer (c) polybutene (d) obtained by hydrogenating a block copolymer comprising a polymer block mainly composed of a polymer block and a conjugated diene comprising isoprene and having a specific weight average molecular weight
  • the thermoplastic polymer compositions of Examples 1 and 2 containing the propylene polymer (e) have good gas barrier properties, fluidity, heat resistance, Surface properties, mechanical properties such as tensile strength it can be seen that.
  • the weight average molecular weight of the hydrogenated block copolymer (b) is low, the thermoplastic polymer composition of Comparative Example 1 is inferior in surface characteristics, heat resistance and tensile strength.
  • thermoplastic polymer composition of Comparative Example 2 is inferior in surface properties, heat resistance and tensile strength because the weight average molecular weight of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is low. . Furthermore, since the thermoplastic polymer composition of Comparative Example 3 does not contain the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c), it is inferior in surface characteristics, fluidity and tensile strength. . Furthermore, the thermoplastic polymer composition of Comparative Example 4 includes an isobutylene-based crosslinked thermoplastic polymer composition (a) obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal, and a hydrogenated block copolymer. Since (c) is not contained, it is inferior to gas barrier property and heat resistance.
  • thermoplastic polymer composition of the present invention is excellent in mechanical properties such as gas barrier properties, fluidity, heat resistance, surface properties, and tensile strength, so that it is a medical member, automobile, vehicle material, building material, electric / electronic Products, food containers, daily necessities, packing materials, hoses, tubes in all other fields, automobile interior materials, exterior materials, flooring materials, home appliance parts, OA equipment and other electrical and electronic parts, food appliances, audio It can be effectively used in a wide range of applications such as equipment, various switches, optical cables, sports equipment, shoes, building materials, toys, and stationery.

Abstract

[Problem] To provide: a thermoplastic polymer composition having excellent mechanical properties including gas barrier properties, fluidability, heat resistance, surface properties and tensile strength; and a packing material, a medical member, a tube and a hose, each of which is produced using a thermoplastic polymer composition. [Solution] A thermoplastic polymer composition comprising: 100 parts by mass of (a) an isobutylene-type cross-linked polymer which is produced by cross-linking an isobutylene-type polymer having an alkenyl group at a terminal thereof; 10 to 100 parts by mass of (b) a hydrogenated block copolymer which is produced by the hydrogenation of a block copolymer that comprises a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene, and which has a weight average molecular weight of 150000 to 500000; 10 to 100 parts by mass of (c) a hydrogenated block copolymer which is produced by the hydrogenation of a block copolymer that comprises a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene, and which has a weight average molecular weight of 200000 to 500000; 5 to 100 parts by mass of (d) a polybutene; and 1 to 100 parts by mass of (e) a propylene-type polymer.

Description

ガスバリア性に優れた熱可塑性重合体組成物Thermoplastic polymer composition having excellent gas barrier properties
　本発明はガスバリア性に優れた熱可塑性重合体組成物、および該熱可塑性重合体組成物を用いたパッキン材や医療用部材、チューブ、ホースに関する。 The present invention relates to a thermoplastic polymer composition excellent in gas barrier properties, and a packing material, a medical member, a tube, and a hose using the thermoplastic polymer composition.
　熱可塑性重合体組成物は、加硫工程を必要とせず、熱可塑性樹脂と同様に成形加工が可能であることから、自動車部品、家電製品部品、玩具、スポーツ用品、医療用品、日用品、雑貨などの広い分野で使用されている。このような熱可塑性重合体組成物の中でも、末端にアルケニル基を有するイソブチレン系重合体は、優れたガスバリア性と耐熱性を利用して、広範な用途に使用される。また、ビニル芳香族化合物―共役ジエン化合物の水添ブロック共重合体を用いた熱可塑性重合体組成物は柔軟性、ゴム弾性、優れたオイル保持性、力学強度に優れる物性を利用して、様々な用途に使用される。例えば、特許文献１及び２には、イソブチレン系重合体、ポリオレフィン系重合体及び軟化剤を含有する熱可塑性重合体組成物が開示されている。しかし、特許文献１に記載される熱可塑性重合体組成物は、引張強度等の力学物性、表面特性については十分に満足できるものではなく、更なる改善が望まれている。一方、特許文献２には記載される熱可塑性重合体組成物は、ガスバリア性、表面特性、引張強度等の力学物性については記載されておらず、満足できるものではない。 Thermoplastic polymer compositions do not require a vulcanization process and can be molded in the same way as thermoplastic resins, so automobile parts, home appliance parts, toys, sports equipment, medical supplies, daily necessities, miscellaneous goods, etc. Is used in a wide range of fields. Among such thermoplastic polymer compositions, isobutylene-based polymers having an alkenyl group at the terminal are used for a wide range of applications by utilizing excellent gas barrier properties and heat resistance. In addition, thermoplastic polymer compositions using hydrogenated block copolymers of vinyl aromatic compounds and conjugated diene compounds have various properties that utilize flexibility, rubber elasticity, excellent oil retention, and excellent mechanical strength. Used for various purposes. For example, Patent Documents 1 and 2 disclose thermoplastic polymer compositions containing an isobutylene polymer, a polyolefin polymer, and a softening agent. However, the thermoplastic polymer composition described in Patent Document 1 is not satisfactory in terms of mechanical properties such as tensile strength and surface properties, and further improvement is desired. On the other hand, the thermoplastic polymer composition described in Patent Document 2 is not satisfactory because it does not describe mechanical properties such as gas barrier properties, surface characteristics, and tensile strength.
ＷＯ２００９／０１３９４５号パンフレットWO2009 / 013945 pamphlet 特開２０１０－２２７２８５号公報JP 2010-227285 A
　本発明の目的は、ガスバリア性、流動性、耐熱性、表面特性、引張強度等の力学物性に優れる熱可塑性重合体組成物および熱可塑性重合体組成物を用いたパッキン材、医療用部材、チューブ、およびホースを提供することにある。 An object of the present invention is to provide a thermoplastic polymer composition excellent in mechanical properties such as gas barrier properties, fluidity, heat resistance, surface properties, and tensile strength, and a packing material, a medical member, and a tube using the thermoplastic polymer composition And to provide a hose.
　本発明者らが鋭意検討した結果、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物と、特定の分子量と構造を有するビニル芳香族化合物を主体とする重合体ブロックと特定の共役ジエンを主体とするブロック共重合体を水素添加して得られるブロック共重合体と、ポリブテンとプロピレン系重合体を特定の割合で配合させることにより、上記課題を解決できることを見出し本発明に至った。 As a result of intensive studies by the present inventors, a polymer block mainly composed of an isobutylene-based crosslinked polymer obtained by crosslinking an isobutylene-based polymer having an alkenyl group at a terminal, and a vinyl aromatic compound having a specific molecular weight and structure. And the block copolymer obtained by hydrogenating the block copolymer mainly composed of a specific conjugated diene, and the polybutene and the propylene polymer are blended at a specific ratio, and the above-mentioned problems can be solved. Invented.
　すなわち、本発明は、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）：１００質量部、
ビニル芳香族化合物を主体とする重合体ブロックと、イソプレンとブタジエンとからなる共役ジエンを主体とする重合体ブロックとからなるブロック共重合体を水素添加して得られ、重量平均分子量が１５００００～５０００００である水添ブロック共重合体（ｂ）：１０～１００質量部、
ビニル芳香族化合物を主体とする重合体ブロックと、イソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体を水素添加して得られ、重量平均分子量が２０００００～５０００００である水添ブロック共重合体（ｃ）：１０～１００質量部、ポリブテン（ｄ）：５～１００質量部、および
プロピレン系重合体（ｅ）：１～１００質量部、
を含有してなる熱可塑性重合体組成物である。 That is, the present invention provides an isobutylene-based crosslinked polymer (a) obtained by crosslinking an isobutylene-based polymer having an alkenyl group at a terminal: 100 parts by mass,
A block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene is obtained by hydrogenation, and has a weight average molecular weight of 150,000 to 500,000. Hydrogenated block copolymer (b): 10 to 100 parts by mass
A hydrogenated hydrogen block having a weight average molecular weight of 200,000 to 500,000, obtained by hydrogenating a polymer block mainly composed of a vinyl aromatic compound and a block copolymer composed mainly of a conjugated diene composed of isoprene. Block copolymer (c): 10 to 100 parts by mass, polybutene (d): 5 to 100 parts by mass, and propylene polymer (e): 1 to 100 parts by mass,
Is a thermoplastic polymer composition.
　本発明は、該熱可塑性重合体組成物を用いたパッキン材、医療用部材、チューブおよびホースも包含する。 The present invention also includes a packing material, a medical member, a tube, and a hose using the thermoplastic polymer composition.
　本発明によれば、良好なガスバリア性、良流動性、耐熱性、表面特性、引張強度等の力学物性を有する熱可塑性重合体組成物を提供できる。 According to the present invention, a thermoplastic polymer composition having good physical properties such as gas barrier properties, good fluidity, heat resistance, surface properties, and tensile strength can be provided.
　本発明の熱可塑性重合体組成物は、イソブチレン系架橋重合物（ａ）、ビニル芳香族化合物を主体とする重合体ブロックとイソプレンとブタジエンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｂ）、ビニル芳香族化合物を主体とする重合体ブロックとイソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｃ）、ポリブテン（ｄ）、プロピレン系重合体（ｅ）から構成される。 The thermoplastic polymer composition of the present invention comprises a block copolymer comprising an isobutylene-based crosslinked polymer (a), a polymer block mainly composed of a vinyl aromatic compound, and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene. Hydrogenated block copolymer (b) obtained by hydrogenating a polymer, block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene And hydrogenated block copolymer (c) obtained by hydrogenation, polybutene (d), and propylene polymer (e).
＜イソブチレン系架橋重合物（ａ）＞
　本発明の熱可塑性重合体組成物を構成するイソブチレン系架橋重合物（ａ）は、末端にアルケニル基を有するイソブチレン系重合体を架橋することにより得られる。ここで、末端にアルケニル基を有するイソブチレン系重合体とは、イソブチレンブロックからなり、末端にアルケニル基を有する重合体である。イソブチレン系重合体におけるイソブチレン単位の含有量は、７０重量％以上が好ましく、９０重量％以上がより好ましい。イソブチレン単位の含有量がこの範囲内であると、本発明の熱可塑性重合体組成物のガスバリア性がより向上する。イソブチレン系重合体には、イソブチレンの他に、本発明の効果を損なわない範囲において他のモノマーが共重合されていてもよい。該他のモノマーとしては、１－ブテン、ペンテン、ヘキセン、ブタジエン、イソプレン、メチルビニルエーテル等のカチオン重合性モノマーを例示することができる。アルケニル基とは、炭素―炭素二重結合を有する基であれば、なんら制限なく使用できる。具体的には、ビニル基、アリル基、メチルビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、などが挙げられる。 <Isobutylene-based crosslinked polymer (a)>
The isobutylene-based crosslinked polymer (a) constituting the thermoplastic polymer composition of the present invention can be obtained by crosslinking an isobutylene-based polymer having an alkenyl group at the terminal. Here, the isobutylene polymer having an alkenyl group at the terminal is a polymer comprising an isobutylene block and having an alkenyl group at the terminal. The content of isobutylene units in the isobutylene polymer is preferably 70% by weight or more, and more preferably 90% by weight or more. When the content of the isobutylene unit is within this range, the gas barrier property of the thermoplastic polymer composition of the present invention is further improved. In addition to isobutylene, other monomers may be copolymerized with the isobutylene polymer as long as the effects of the present invention are not impaired. Examples of the other monomer include cationic polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. The alkenyl group can be used without any limitation as long as it is a group having a carbon-carbon double bond. Specific examples include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
　末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物は、ポリブテンとポリオレフィン系重合体が含まれた状態で架橋することが好ましい。
　ポリブテンは、柔軟性、成形加工性を付与する目的で添加される。ポリオレフィン系重合体は、流動性を付与する目的で添加される。ポリオレフィン系重合体はプロピレン系重合体とエチレン系重合体があげられる。プロピレン系重合体としては、例えばホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレン、アタクチックポリプロピレン、シンジオタクチックポリプロピレン等を使用することができる。エチレン系重合体としては、例えば中密度ポリエチレン、低密度ポリエチレン（ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のエチレン単独重合体；エチレン・１－ブテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－ヘプテン共重合体、エチレン・１－オクテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・１－ノネン共重合体、エチレン・１－デセン共重合体等のエチレン・α－オレフィン共重合体等を使用することができる。 The isobutylene-based crosslinked polymer obtained by crosslinking an isobutylene-based polymer having an alkenyl group at the terminal is preferably crosslinked in a state where the polybutene and the polyolefin-based polymer are included.
Polybutene is added for the purpose of imparting flexibility and moldability. The polyolefin polymer is added for the purpose of imparting fluidity. Examples of the polyolefin polymer include a propylene polymer and an ethylene polymer. As the propylene polymer, for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used. Examples of the ethylene polymer include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc. An ethylene / α-olefin copolymer or the like can be used.
　架橋の方法としては、架橋剤および／または架橋助剤を用いて行う方法であってもよく、架橋剤としては、有機過酸化物を用いて反応する方法、ヒドロシリル基含有化合物を用いて反応する方法が挙げられる。架橋密度を高める観点から、ヒドロシリル基含有化合物を用いる方法が最も好ましい。 The cross-linking method may be a method using a cross-linking agent and / or a cross-linking aid, and as the cross-linking agent, a method using a peroxide or a hydrosilyl group-containing compound. A method is mentioned. From the viewpoint of increasing the crosslinking density, a method using a hydrosilyl group-containing compound is most preferable.
　さらには、本発明の熱可塑性重合体組成物が所望の効用が得られる場合においては限定されないものの、末端にアルケニル基を有するイソブチレン系重合体にポリブテンとポリオレフィン系重合体を混合しさらに別の架橋剤または架橋助剤を加え混合しながら架橋を行ういわゆる動的架橋によってイソブチレン系架橋重合物が得られることが、得られる熱可塑性重合体組成物の生産性や品質の均一性等の点から好ましい。より具体的には、二軸押出機を使用して、溶融混練時に架橋を行ってイソブチレン系架橋重合物が得られることが好ましい一例である。 Furthermore, although the thermoplastic polymer composition of the present invention is not limited in the case where the desired utility is obtained, the polybutylene and the polyolefin polymer are further mixed with the isobutylene polymer having an alkenyl group at the terminal, and further crosslinked. It is preferable from the viewpoint of productivity and quality uniformity of the obtained thermoplastic polymer composition that the so-called dynamic crosslinking in which crosslinking is performed while adding an agent or a crosslinking aid and mixing is preferable. . More specifically, a preferred example is that an isobutylene-based crosslinked polymer is obtained by performing crosslinking at the time of melt kneading using a twin-screw extruder.
＜ビニル芳香族化合物を主体とする重合体ブロックとイソプレンとブタジエンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｂ）＞
　水添ブロック共重合体（ｂ）は、ビニル芳香族化合物を主体とする重合体ブロック（Ａ）と、イソプレンとブタジエンからなる共役ジエン化合物からなる重合体ブロック（Ｂ）とを含有するブロック共重合体を水素添加して得られるものである。
　前記重合体ブロック（Ａ）を構成するビニル芳香族化合物としては、例えばスチレン、α－メチルスチレン、ｏ，ｍ若しくはｐ－メチルスチレン、１，３－ジメチルスチレン、ビニルナフタレン、ビニルアントラセン等が挙げられる。これらの中でも、スチレンおよびα－メチルスチレンが好ましい。ビニル芳香族化合物は１種を単独で用いてもよく、２種類以上を併用してもよい。 <Hydrogenated block copolymer (b) obtained by hydrogenating a block copolymer consisting of a polymer block mainly composed of vinyl aromatic compound and a polymer block mainly composed of conjugated diene composed of isoprene and butadiene >
The hydrogenated block copolymer (b) is a block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) composed of a conjugated diene compound composed of isoprene and butadiene. It is obtained by hydrogenating the coalescence.
Examples of the vinyl aromatic compound constituting the polymer block (A) include styrene, α-methylstyrene, o, m or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. . Of these, styrene and α-methylstyrene are preferred. A vinyl aromatic compound may be used individually by 1 type, and may use 2 or more types together.
　前記水添ブロック共重合体（ｂ）におけるビニル芳香族化合物の含有量は５～７５質量％が好ましく、５～５０質量％がより好ましい。ビニル芳香族化合物の含有量がこの範囲内であると、本発明の熱可塑性重合体組成物のゴム弾性がより向上する。 The content of the vinyl aromatic compound in the hydrogenated block copolymer (b) is preferably 5 to 75% by mass, and more preferably 5 to 50% by mass. When the content of the vinyl aromatic compound is within this range, the rubber elasticity of the thermoplastic polymer composition of the present invention is further improved.
　前記重合体ブロック（Ｂ）を構成する共役ジエン化合物としては、例えば１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、１，３－ヘキサジエン等が挙げられる。共役ジエン化合物は、ガスバリア性及び引張強度等の力学物性及び表面性の観点からイソプレンと１，３－ブタジエンの混合物が最も好ましい。 Examples of the conjugated diene compound constituting the polymer block (B) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. The conjugated diene compound is most preferably a mixture of isoprene and 1,3-butadiene from the viewpoint of mechanical properties such as gas barrier properties and tensile strength, and surface properties.
　前記水添ブロック共重合体（ｂ）における共役ジエン化合物に由来する炭素－炭素二重結合の５０％以上が水素添加されていることが好ましく、７５％以上が水素添加されていることがより好ましく、９５％以上が水素添加されていることが特に好ましい。 50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (b) are preferably hydrogenated, and more preferably 75% or more are hydrogenated. It is particularly preferable that 95% or more is hydrogenated.
　前記水添ブロック共重合体（ｂ）は、重合体ブロック（Ａ）と重合体ブロック（Ｂ）とをそれぞれ少なくとも１個含有していればよいが、耐熱性、力学物性等の観点から、重合体ブロック（Ａ）を２個以上、重合体ブロック（Ｂ）を１個以上含有していることが好ましい。重合体ブロック（Ａ）と重合体ブロック（Ｂ）の結合様式は、線状、分岐状あるいはこれらの任意の組み合わせであってもよいが、重合体ブロック（Ａ）をＡで、重合体ブロック（Ｂ）をＢで表したとき、Ａ－Ｂ－Ａで示されるトリブロック構造や、（Ａ－Ｂ）、（Ａ－Ｂ）ｎ－Ａ、（ここでｎは２以上の整数を表す）で示すマルチブロック共重合体などを挙げることができ、これらの中でも、Ａ－Ｂ－Ａで示されるトリブロック構造のものが、耐熱性、力学物性、取り扱い性等の点で特に好ましい。 The hydrogenated block copolymer (b) may contain at least one polymer block (A) and polymer block (B), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable to contain 2 or more combined blocks (A) and 1 or more polymer blocks (B). The bonding mode of the polymer block (A) and the polymer block (B) may be linear, branched, or any combination thereof. The polymer block (A) is A, and the polymer block ( When B) is represented by B, the triblock structure represented by ABA, or (AB), (AB) n -A (where n represents an integer of 2 or more) Among them, a triblock structure represented by ABA is particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
　前記ブロック共重合体（ｂ）の重量平均分子量は１５００００～５０００００の範囲内であることが成形加工性と耐熱性の観点から重要であって、１５００００～４０００００の範囲内が好ましい。なお、本明細書でいう重量平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によって求めたポリスチレン換算の重量平均分子量をいう。 The weight average molecular weight of the block copolymer (b) is in the range of 150,000 to 500,000 from the viewpoint of molding processability and heat resistance, and is preferably in the range of 150,000 to 400,000. In addition, the weight average molecular weight as used in this specification means the weight average molecular weight of polystyrene conversion calculated | required by the gel permeation chromatography (GPC) measurement.
　測定条件：
ＧＰＣ；ＬＣ　Ｓｏｌｕｔｉｏｎ　（ＳＨＩＭＡＤＺＵ製）
検出器：示差屈折率計　ＲＩＤ－１０Ａ（ＳＨＩＭＡＤＺＵ製）
カラム：ＴＳＫｇｅｌＧ４０００Ｈｘｌを２本直列（ＴＯＳＯＨ製）
ガードカラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎＨｘｌ－Ｌ（ＴＯＳＯＨ製）
溶媒：テトラヒドロフラン
温度：４０℃
流速：１ｍｌ／ｍｉｎ
濃度：２ｍｇ／ｍｌ Measurement condition:
GPC; LC Solution (manufactured by SHIMADZU)
Detector: differential refractometer RID-10A (manufactured by SHIMADZU)
Column: TSKgel G4000Hxl in series (made by TOSOH)
Guard column: TSK guard column Hxl-L (manufactured by TOSOH)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 1 ml / min
Concentration: 2 mg / ml
　本発明の熱可塑性重合体組成物において、水添ブロック共重合体（ｂ）の配合量は、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）１００質量部に対して１０～１００質量部であり、好適には１０～８０質量部である。１０質量部未満では流動性が劣り、成形性が困難となるばかりか、成形体が得られたとしても、表面性が膠着するようになり、表面性が著しく劣ったものとなる。一方、１００質量部を超えるとガスバリア性が低下する。 In the thermoplastic polymer composition of the present invention, the blended amount of the hydrogenated block copolymer (b) is such that the isobutylene crosslinked polymer (a) obtained by crosslinking an isobutylene polymer having an alkenyl group at the terminal is 100 masses. 10 to 100 parts by weight, and preferably 10 to 80 parts by weight with respect to the part. If the amount is less than 10 parts by mass, not only the fluidity is inferior and the moldability becomes difficult, but even if a molded product is obtained, the surface property becomes sticky and the surface property becomes extremely inferior. On the other hand, when it exceeds 100 mass parts, gas barrier property will fall.
＜ビニル芳香族化合物を主体とする重合体ブロックとイソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｃ）＞
　水添ブロック共重合体（ｃ）は、ビニル芳香族化合物からなる重合体ブロック（Ｃ）と、イソプレンからなる共役ジエン化合物からなる重合体ブロック（Ｄ）とを含有するブロック共重合体を水素添加して得られるものである。
　前記重合体ブロック（Ｃ）を構成するビニル芳香族化合物としては、例えばスチレン、α－メチルスチレン、ｏ，ｍ若しくはｐ－メチルスチレン、１，３－ジメチルスチレン、ビニルナフタレン、ビニルアントラセン等が挙げられる。これらの中でも、スチレンおよびα－メチルスチレンが好ましい。ビニル芳香族化合物は１種を単独で用いてもよく、２種類以上を併用してもよい。また重合体ブロック（Ａ）を構成するビニル芳香族化合物と同一であってもよく、異なっていてもよい。 <Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer consisting of a polymer block mainly composed of vinyl aromatic compound and a polymer block mainly composed of conjugated diene composed of isoprene>
Hydrogenated block copolymer (c) is a hydrogenated block copolymer containing a polymer block (C) made of a vinyl aromatic compound and a polymer block (D) made of a conjugated diene compound made of isoprene. Is obtained.
Examples of the vinyl aromatic compound constituting the polymer block (C) include styrene, α-methylstyrene, o, m or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. . Of these, styrene and α-methylstyrene are preferred. A vinyl aromatic compound may be used individually by 1 type, and may use 2 or more types together. Further, it may be the same as or different from the vinyl aromatic compound constituting the polymer block (A).
　水添ブロック共重合体（ｃ）におけるビニル芳香族化合物の含有量は５～７５質量％が好ましく、５～５０質量％がより好ましい。ビニル芳香族化合物の含有量がこの範囲内であると、本発明の熱可塑性重合体組成物のゴム弾性がより向上する。 The content of the vinyl aromatic compound in the hydrogenated block copolymer (c) is preferably 5 to 75% by mass, and more preferably 5 to 50% by mass. When the content of the vinyl aromatic compound is within this range, the rubber elasticity of the thermoplastic polymer composition of the present invention is further improved.
　前記水添ブロック共重合体（ｃ）における共役ジエン化合物としては、例えば１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、１，３－ヘキサジエン等が挙げられる。共役ジエン化合物は、１種を単独で用いてもよく、２種類以上を併用してもよい。これらの中でも、ガスバリア性及び引張強度等の力学物性及び表面性の観点から共役ジエン化合物としてイソプレンを用いるのがより好ましい。 Examples of the conjugated diene compound in the hydrogenated block copolymer (c) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Is mentioned. A conjugated diene compound may be used individually by 1 type, and may use 2 or more types together. Among these, it is more preferable to use isoprene as the conjugated diene compound from the viewpoints of mechanical properties such as gas barrier properties and tensile strength, and surface properties.
　前記水添ブロック共重合体（ｃ）における共役ジエン化合物に由来する炭素－炭素二重結合の５０％以上が水素添加されていることが好ましく、７５％以上が水素添加されていることがより好ましく、９５％以上が水素添加されていることが特に好ましい。 50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (c) are preferably hydrogenated, and more preferably 75% or more are hydrogenated. It is particularly preferable that 95% or more is hydrogenated.
　前記水添ブロック共重合体（ｃ）は、重合体ブロック（Ｃ）と重合体ブロック（Ｄ）とをそれぞれ少なくとも１個含有していればよいが、耐熱性、力学物性等の観点から、重合体ブロック（Ｃ）を２個以上、重合体ブロック（Ｄ）を１個以上含有していることが好ましい。重合体ブロック（Ｃ）と重合体ブロック（Ｄ）の結合様式は、線状、分岐状あるいはこれらの任意の組み合わせであってもよいが、重合体ブロック（Ｃ）をＣで、重合体ブロック（Ｄ）をＤで表したとき、Ｃ－Ｄ－Ｃで示されるトリブロック構造や、（Ｃ－Ｄ）ｎ、（Ｃ－Ｄ）ｎ－Ｃ、（ここでｎは２以上の整数を表す）で示すマルチブロック共重合体などを挙げることができ、これらの中でも、Ｃ－Ｄ－Ｃで示されるトリブロック構造のものが、耐熱性、力学物性、取り扱い性等の点で特に好ましい。 The hydrogenated block copolymer (c) only needs to contain at least one polymer block (C) and one polymer block (D), but from the viewpoint of heat resistance, mechanical properties, etc. It is preferable that two or more united blocks (C) and one or more polymer blocks (D) are contained. The bonding mode of the polymer block (C) and the polymer block (D) may be linear, branched, or any combination thereof. The polymer block (C) is C, the polymer block ( When D) is represented by D, a triblock structure represented by CDC, or (CD) n , (CD) n -C, where n represents an integer of 2 or more Among them, those having a triblock structure represented by C—D—C are particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
　前記ブロック共重合体（ｃ）の重量平均分子量は２０００００～５０００００の範囲内であることが成形加工性と耐熱性の観点から重要であって、２０００００～４０００００の範囲内が好ましい。 The weight average molecular weight of the block copolymer (c) is important in the range of 200,000 to 500,000 from the viewpoint of molding processability and heat resistance, and preferably in the range of 200,000 to 400,000.
　本発明の熱可塑性重合体組成物において、ブロック共重合体（ｃ）の配合量は、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）１００質量部に対して１０～１００質量部であり、好適には１０～８０質量部である。ブロック共重合体（ｃ）が１０質量部未満では流動性が劣り、ブロック共重合体（ｃ）が１００質量部を超えるとガスバリア性が低下する。 In the thermoplastic polymer composition of the present invention, the blending amount of the block copolymer (c) is 100 parts by mass of the isobutylene crosslinked polymer (a) obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal. The amount is 10 to 100 parts by weight, preferably 10 to 80 parts by weight. When the block copolymer (c) is less than 10 parts by mass, the fluidity is inferior, and when the block copolymer (c) exceeds 100 parts by mass, the gas barrier property is lowered.
　本発明の熱可塑性重合体組成物において、水添ブロック共重合体（ｂ）と水添ブロック共重合体（ｃ）との質量の和は、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）１００質量部に対して、２０～１６０質量部であることが好ましく、２０～１２０質量部であることがより好ましく、２０～１００質量部であることが最も好ましい。イソブチレン系架橋重合物（ａ）１００質量部に対して、水添ブロック共重合体（ｂ）と水添ブロック共重合体（ｃ）との質量の和が２０質量部未満では流動性が劣り、１６０質量部を超えるとガスバリア性が低下する。
　また、水添ブロック共重合体（ｂ）と水添ブロック共重合体（ｃ）との質量の比は９０／１０～１０／９０の範囲であることが好ましい。 In the thermoplastic polymer composition of the present invention, the sum of the masses of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal. It is preferably 20 to 160 parts by mass, more preferably 20 to 120 parts by mass, and most preferably 20 to 100 parts by mass with respect to 100 parts by mass of the isobutylene-based crosslinked polymer (a). preferable. When the sum of the masses of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is less than 20 parts by mass with respect to 100 parts by mass of the isobutylene-based crosslinked polymer (a), the fluidity is inferior. If it exceeds 160 parts by mass, the gas barrier properties will be reduced.
The mass ratio of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is preferably in the range of 90/10 to 10/90.
＜ポリブテン（ｄ）＞
　ポリブテン（ｄ）としては、得られる熱可塑性重合体組成物のガスバリア性及び表面性の観点から、１００℃で測定した動粘度が１００ｍｍ２／ｓ以上であるものが好ましく、１５０ｍｍ２／ｓ以上であるものがより好ましい。動粘度が１００ｍｍ２／ｓ以上であれば、本発明の熱可塑性重合体組成物を成形品に加工した際に、オイルのブリードが極めて少なくなり、特にガスバリア性に優れた熱可塑性重合体組成物が得られる。なお、本明細書でいう動粘度とは、ＡＳＴＭ　Ｄ４４５に準じて測定した値である。 <Polybutene (d)>
The polybutene (d) is preferably one having a kinematic viscosity measured at 100 ° C. of 100 mm 2 / s or more from the viewpoint of gas barrier properties and surface properties of the thermoplastic polymer composition obtained, and 150 mm 2 / s or more. Some are more preferred. If the kinematic viscosity is 100 mm 2 / s or more, when the thermoplastic polymer composition of the present invention is processed into a molded product, the oil bleed is extremely reduced, and the thermoplastic polymer composition particularly excellent in gas barrier properties. Is obtained. In addition, kinematic viscosity as used in this specification is the value measured according to ASTM D445.
　本発明の熱可塑性重合体組成物において、ポリブテン（ｄ）の配合量は、末端にアルケニル基を有するイソブチレン系重合体を架橋してからなるイソブチレン系架橋重合物（ａ）１００質量部に対して５～１００質量部であり、好適には１０～８０質量部である。ポリブテンが５質量部未満では流動性が劣り、１００質量部を超えると表面性及び引張強さ等の力学物性が低下する。 In the thermoplastic polymer composition of the present invention, the amount of polybutene (d) is based on 100 parts by mass of the isobutylene crosslinked polymer (a) obtained by crosslinking the isobutylene polymer having an alkenyl group at the terminal. The amount is 5 to 100 parts by mass, preferably 10 to 80 parts by mass. If the polybutene is less than 5 parts by mass, the fluidity is inferior, and if it exceeds 100 parts by mass, the mechanical properties such as surface properties and tensile strength are lowered.
＜プロピレン系重合体（ｅ）＞
　本発明の熱可塑性重合体組成物において、プロピレン系重合体（ｅ）は、例えばホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレン、アタクチックポリプロピレン、シンジオタクチックポリプロピレン等を使用することができる。中でも、ホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレンを用いるのが好ましい。これらのプロピレン系重合体は、１種類を単独で使用しても、２種類以上を併用してもよい。 <Propylene polymer (e)>
In the thermoplastic polymer composition of the present invention, as the propylene polymer (e), for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene or the like can be used. Among these, homopolypropylene, random polypropylene, and block polypropylene are preferably used. These propylene polymers may be used alone or in combination of two or more.
　プロピレン系重合体（ｅ）の２３０℃、２１Ｎの条件下で測定されるメルトフローレート（ＭＦＲ）は、５ｇ／１０ｍｉｎ以上であることが好ましい。ＭＦＲが５ｇ／１０ｍｉｎ未満であると、得られる熱可塑性重合体組成物の流動性が低下し、好ましくない。なお、当該ＭＦＲはＪＩＳ　Ｋ７２１０に準拠して測定することができる。 The melt flow rate (MFR) measured under conditions of 230 ° C. and 21 N of the propylene polymer (e) is preferably 5 g / 10 min or more. If the MFR is less than 5 g / 10 min, the fluidity of the resulting thermoplastic polymer composition is undesirably lowered. The MFR can be measured according to JIS K7210.
　本発明の熱可塑性重合体組成物において、プロピレン系重合体（ｅ）の配合量は、末端にアルケニル基を有するイソブチレン系重合体を動的架橋してからなるイソブチレン系架橋重合物（ａ）１００質量部に対して１～１００質量部であり、好適には１～８０質量部である。プロピレン系重合体（ｅ）が１質量部未満では流動性が劣り、１００質量部を超えると柔軟性が低下する。 In the thermoplastic polymer composition of the present invention, the amount of the propylene-based polymer (e) is such that the isobutylene-based crosslinked polymer (a) 100 obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal is used. The amount is 1 to 100 parts by weight, preferably 1 to 80 parts by weight with respect to the parts by weight. When the propylene polymer (e) is less than 1 part by mass, the fluidity is inferior, and when it exceeds 100 parts by mass, the flexibility is lowered.
　本発明の熱可塑性重合体組成物は、上記の成分の他に、用途に応じて各種のブロッキング防止剤、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、滑剤、結晶核剤、発泡剤、着色剤等を含有することも可能である。ここで、酸化防止剤としては、例えば、２,６－ジｔｅｒｔ－ブチル－ｐ－クレゾール、２,６－ジｔｅｒｔ－ブチルフェノール、２,４－ジメチル－６－ｔｅｒｔ－ブチルフェノール、４,４’－ジヒドロキシジフェニル、トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、テトラキス［メチレン－３－（３,５－ジｔｅｒｔ－ブチル－4－ヒドロキシフェニル）プロピオネート］メタン、３,９ビス｛２－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］－１,１－ジメチルエチル｝－２,４,８,１０－テトラオキサスピロ－５,５－ウンデカンなどのフェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等を使用することができる。中でもフェノール系酸化防止剤、ホスファイト系酸化防止剤が特に好ましい。酸化防止剤は、本発明の熱可塑性重合体組成物に含まれる上記成分（ａ）～（ｅ）の合計１００質量部に対して、０．０１～３．０質量部であることが好ましく、０．０５～１．０質量部であることがより好ましい。 In addition to the above components, the thermoplastic polymer composition of the present invention includes various anti-blocking agents, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, depending on applications. It is also possible to contain a foaming agent, a colorant and the like. Here, as the antioxidant, for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 Bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro-5,5 -Phenol antioxidants such as undecane, phosphite antioxidants, thioether antioxidants, etc. can be used. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the above components (a) to (e) contained in the thermoplastic polymer composition of the present invention. More preferred is 0.05 to 1.0 part by mass.
　本発明の熱可塑性重合体組成物の製造方法としては、通常の樹脂組成物の製造あるいはゴム組成物の製造に際して用いられる方法が採用でき、単軸押出機、二軸押出機、バンバリーミキサー、加熱ロール、各種ニーダー等の溶融混練機を用いて各成分を均一に混合することにより製造できる。加工機の設定温度は１５０℃～３００℃の中から任意に選ぶことができる。 As a method for producing the thermoplastic polymer composition of the present invention, a method used for producing a normal resin composition or a rubber composition can be employed, and a single screw extruder, twin screw extruder, Banbury mixer, heating It can manufacture by mixing each component uniformly using melt kneaders, such as a roll and various kneaders. The set temperature of the processing machine can be arbitrarily selected from 150 ° C to 300 ° C.
　本発明の熱可塑性重合体組成物は、各種成形法、例えば、押出成形、射出成形、中空成形、圧縮成形、カレンダー成形などの公知の方法を用いて、シート状、フィルム状、チューブ状などの任意の形状の成形体に成形することができる。また、本発明の熱可塑性重合体組成物は、二色成形法、インサート成形法、共押出などにより、プラスチック、布帛等の他の材料と複合化してなる複合成形体とすることも可能である。 The thermoplastic polymer composition of the present invention may be formed into various sheet forming methods such as extrusion, injection molding, hollow molding, compression molding, calendar molding, and the like using a known method such as sheet, film, and tube. It can be formed into a molded body having an arbitrary shape. In addition, the thermoplastic polymer composition of the present invention can also be made into a composite molded body obtained by combining with other materials such as plastic and fabric by two-color molding method, insert molding method, co-extrusion and the like. .
＜パッキン材について＞
　本発明の熱可塑性重合体組成物からなるパッキン材は、自動車、車両材料、建築材料、電気・電子製品、食品容器、日用品、その他のあらゆる分野において、水密性、気密性等ガスバリア性が必要な部位に使用されるパッキン材として好適に使用することができる。　例えば、自動車、電機・電子製品等のあらゆる機器に電気二重層コンデンサが使用されているが、本発明のパッキン材を電解液の封口と導電性材料の絶縁のためのパッキンに使用した電気二重層コンデンサは、ガスバリア性が良好であって、電解液のコンデンサ外への漏出や揮発を生じにくく、電気二重層コンデンサの寿命に優れる特徴を有する。
　また本発明のパッキン材を食品容器に用いると、大気中の酸素ガスが食品容器内に透過したり、容器内の食品中の香味成分が容器外に抜けたりすることが少なくなるため、食品容器用のパッキンとしても優れている。 <About packing material>
The packing material made of the thermoplastic polymer composition of the present invention requires gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and all other fields. It can be suitably used as a packing material used for the part. For example, electric double layer capacitors are used in all devices such as automobiles, electric appliances, and electronic products. The electric double layer is formed by using the packing material of the present invention as a seal for sealing an electrolyte and insulating a conductive material. Capacitors have a good gas barrier property, are less likely to cause leakage and volatilization of the electrolyte solution outside the capacitor, and have an excellent service life of the electric double layer capacitor.
In addition, when the packing material of the present invention is used for a food container, oxygen gas in the atmosphere is less likely to permeate into the food container or flavor components in the food in the container are less likely to escape from the container. It is also excellent as a packing for use.
＜医療用部材について＞
　本発明の熱可塑性重合体組成物からなる医療用部材は、医療用分野において、水密性、気密性等ガスバリア性が必要な医療用部材として好適に使用することができる。
　例えば、医療用輸液ゴム栓、真空採血管などの栓体及びゴム栓、医療用輸液バッグ、医療用シリンジガスケット、プレフィルド用シリンジガスケットに使用することができる。
　本発明の医療用部材は、ガスバリア性に優れ、大気中の酸素ガスが部材内部に透過することやと部材内部に充填された内容物中の揮発性成分が部材外部に揮発することを低減させることが可能となり、内容物の長期保存性に優れる特徴を有する。 <About medical materials>
The medical member comprising the thermoplastic polymer composition of the present invention can be suitably used as a medical member that requires gas barrier properties such as water tightness and air tightness in the medical field.
For example, it can be used for medical infusion rubber stoppers, stoppers and rubber stoppers such as vacuum blood collection tubes, medical infusion bags, medical syringe gaskets, and prefilled syringe gaskets.
The medical member of the present invention has excellent gas barrier properties, and reduces atmospheric oxygen gas permeating into the member and reducing volatile components in the contents filled inside the member from volatilizing outside the member. And has the characteristics of excellent long-term storage of the contents.
＜ホース、チューブについて＞ 
　本発明の熱可塑性重合体組成物からなるホースやチューブは、自動車、車両材料、建築材料、電気・電子製品、食品容器、日用品、その他のあらゆる分野において、水密性、気密性等ガスバリア性が必要な部位に使用されるホース、チューブとして使用することができる。例えば、本発明の熱可塑性重合体組成物からなるチューブをインクジェットプリンター用のインク供給チューブに使用すると、ガスバリア性が良好であるために、チューブ内のインクがチューブ外に蒸発することによる粘度上昇、チューブ外から浸透したガス成分由来の気泡発生を引き起こしてインクの供給を妨げる等の不具合を防ぐことが可能となる。 <About hose and tube>
The hose or tube made of the thermoplastic polymer composition of the present invention requires gas barrier properties such as water tightness and air tightness in automobiles, vehicle materials, building materials, electrical / electronic products, food containers, daily necessities, and other fields. It can be used as a hose or tube used in various parts. For example, when a tube made of the thermoplastic polymer composition of the present invention is used for an ink supply tube for an ink jet printer, since the gas barrier property is good, viscosity increase due to evaporation of ink in the tube to the outside of the tube, It is possible to prevent problems such as the generation of bubbles derived from gas components that have permeated from the outside of the tube and hindering the supply of ink.
　本発明の熱可塑性重合体組成物は、上記に挙げた用途に拘らず、各種工業製品や工業部品として使用することができる。具体的には、インストルメントパネル、センターパネル、センターコンソールボックス、ドアトリム、ピラー、アシストグリップ、ハンドル、エアバックカバー等の自動車内装部品；モール等の自動車外装部品；リモコンスイッチ、ＯＡ機器の各種キートップ、テレビ、ステレオ、掃除機等の家電部品；水中眼鏡、水中カメラのカバー等の水中使用製品；ラック＆ピニオンブーツ、サスペンションブーツ、等速ジョイントブーツ等の自動車機能部品；電線被覆等の電気、電子部品；スポーツシューズ、ファッションサンダル等の履物用途；ベルト、；スポーツ用品；ドア、窓枠材などの建築用資材；各種継手；バルブ部品；等に使用することができる。 The thermoplastic polymer composition of the present invention can be used as various industrial products and industrial parts regardless of the above-mentioned uses. Specifically, automotive interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, and airbag covers; automotive exterior parts such as malls; remote control switches and various key tops for OA equipment Home appliance parts such as TVs, stereos, vacuum cleaners; underwater products such as underwater glasses and underwater camera covers; automotive functional parts such as rack and pinion boots, suspension boots, and constant velocity joint boots; Parts; use for footwear such as sports shoes and fashion sandals; belts; sports equipment; building materials such as doors and window frames; various joints; valve parts;
　以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下の実施例および比較例の物性評価は、以下に示す方法によって行った。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The physical properties of the following examples and comparative examples were evaluated by the methods shown below.
（１）硬度
　実施例及び比較例で得られた熱可塑性重合体組成物を２３０℃で射出成形することによって厚さ２ｍｍのシート形状とし、ＪＩＳ Ｋ ６２５３に準拠してＪＩＳ－Ａ硬度を測定した。
（２）ＭＦＲ
　実施例及び比較例で得られた熱可塑性重合体組成物を用いて、ＪＩＳ　Ｋ　７２１０に準拠して２３０℃、４９Ｎ荷重条件でのＭＦＲ（ｇ／１０ｍｉｎ）を測定し、流動性の指標とした。
（３）破断強度、破断伸度
　実施例及び比較例で得られた熱可塑性重合体組成物を２３０℃で射出成形することによって厚さ２ｍｍのシート形状とした。このシートよりＪＩＳ Ｋ ６２５１に準拠したダンベル３号型の試験片を打ち抜いて作製し、引張試験を２３℃の温度条件および５００ｍｍ／ｍｉｎの引張速度条件下で実施して破断強度、破断伸度を測定した。
（４）耐熱性
　実施例および比較例で得られた熱可塑性重合体組成物を２３０℃で射出成形することによって厚さ２ｍｍのシート形状とした。このシートより、直径２９．０ｍｍ×厚さ１２．５ｍｍの圧縮永久歪み測定用の試験片を作製し、ＪＩＳ　Ｋ　６２６２に準じて、１２０℃の条件下で、圧縮変形量２５％で２４時間放置した後の圧縮永久歪みを測定し、耐熱性の指標とした。
（５）ガスバリア性
　実施例および比較例で得られた熱可塑性重合体組成物を２３０℃で射出成形することによって厚さ１ｍｍのシート形状とした。このシートよりＪＩＳ　Ｋ　７１２６－１、差圧法に準じて、２３℃、試験気体：酸素、条件下で、気体透過度を測定した。また、このシートよりＪＩＳ　Ｚ　０２０８、防湿包装材料の透湿度試験方法（カップ法）に準じて、４０℃、相対湿度９０％の条件下で、透湿度を測定し、ガスバリア性の指標とした。
（６）表面特性
　実施例および比較例で得られた熱可塑性重合体組成物の射出成形シートを指先でなぞることにより、表面性の指標とした（べとつき無し：○、べとつき少し有り：△、べとつき
有り：×）。 (1) Hardness The thermoplastic polymer compositions obtained in the examples and comparative examples were injection molded at 230 ° C. to obtain a sheet shape having a thickness of 2 mm, and the JIS-A hardness was measured in accordance with JIS K 6253. .
(2) MFR
Using the thermoplastic polymer compositions obtained in Examples and Comparative Examples, MFR (g / 10 min) under 230 ° C. and 49 N load conditions was measured according to JIS K 7210, and used as an index of fluidity. .
(3) Breaking strength, breaking elongation The thermoplastic polymer compositions obtained in the examples and comparative examples were injection molded at 230 ° C. to obtain a sheet shape having a thickness of 2 mm. A dumbbell No. 3 type test piece conforming to JIS K 6251 is punched out from this sheet, and a tensile test is performed under a temperature condition of 23 ° C. and a tensile speed condition of 500 mm / min to determine the breaking strength and breaking elongation. It was measured.
(4) Heat resistance The thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to form a sheet shape having a thickness of 2 mm. From this sheet, a test piece for measuring compression set having a diameter of 29.0 mm and a thickness of 12.5 mm was prepared and allowed to stand for 24 hours under a condition of 120 ° C. and 25% compression deformation according to JIS K 6262. The compression set after the measurement was measured and used as an index of heat resistance.
(5) Gas barrier properties The thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to form a sheet shape having a thickness of 1 mm. The gas permeability was measured from this sheet under the conditions of 23 ° C. and test gas: oxygen in accordance with JIS K 7126-1, differential pressure method. Further, according to JIS Z 0208, a moisture permeability test method (cup method) for moisture-proof packaging materials, moisture permeability was measured from this sheet under conditions of 40 ° C. and relative humidity 90%, and used as an index of gas barrier properties.
(6) Surface properties The injection-molded sheets of the thermoplastic polymer compositions obtained in the examples and comparative examples were traced with a fingertip to obtain an index of surface properties (no stickiness: ○, little stickiness: △, stickiness) Yes: x).
＜実施例１～２　及び比較例１～４＞
　二軸押出機（口径４６ｍｍ、Ｌ／Ｄ＝４６）を使用して、下記の各構成成分を表２に示す配合に従って混合した後、２００℃で溶融混練し、ペレット状の熱可塑性重合体組成物を得た。これらの熱可塑性重合体組成物を用いて、射出成形機（２３０℃）で、厚さ２ｍｍ×φ１２０の円盤状のシート形状とした。 <Examples 1 and 2 and Comparative Examples 1 to 4>
Using a twin screw extruder (caliber 46 mm, L / D = 46), the following components were mixed according to the formulation shown in Table 2 and then melt-kneaded at 200 ° C. to form a pellet-shaped thermoplastic polymer composition. I got a thing. These thermoplastic polymer compositions were used to form a disk-like sheet shape having a thickness of 2 mm × φ120 using an injection molding machine (230 ° C.).
＜末端にアルケニル基を有するイソブチレン系重合体を動的架橋してなるイソブチレン系架橋重合物（ａ）＞
・成分（ａ）
製品名：シブスターＰ１１４０Ｂ、製造会社名：（株）カネカ、種類：末端にアルケニル基を有するイソブチレンポリマーからなる化合物に、ポリプロピレンおよびポリブテンを動的架橋してなる、ペレット状の架橋重合物
＜ビニル芳香族化合物を主体とする重合体ブロックとイソプレンとブタジエンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｂ）＞
・成分（ｂ－１）
製品名：セプトン４０５５、製造会社名：（株）クラレ、種類：スチレン－イソプレン・ブタジエン－スチレン型トリブロック共重合体の水添ブロック共重合体、スチレンの含有量：３０質量％、重量平均分子量２７００００
・成分（ｂ－２）
製品名：セプトン４０４４、製造会社名：（株）クラレ、種類：スチレン－イソプレン・ブタジエン－スチレン型トリブロック共重合体の水添ブロック共重合体、スチレンの含有量：３２質量％、重量平均分子量１７００００
・成分（ｂ－３）
製品名：セプトン４０３３、製造会社名：（株）クラレ、種類：スチレン－イソプレン・ブタジエン－スチレン型トリブロック共重合体の水添ブロック共重合体、スチレンの含有量：３０質量％、重量平均分子量９００００
＜ビニル芳香族化合物を主体とする重合体ブロックとイソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られた水添ブロック共重合体（ｃ）＞
・成分（ｃ－１）
製品名：ハイブラー７１３５、製造会社名：（株）クラレ、種類：スチレン－イソプレン－スチレン型トリブロック共重合体の水添ブロック共重合体、スチレンの含有量：３２質量％、重量平均分子量２８００００
・成分（ｃ－２）
製品名：ハイブラー７１２５、製造会社名：（株）クラレ、種類：スチレン－イソプレン－スチレン型トリブロック共重合体の水添ブロック共重合体、スチレンの含有量：２０質量％、重量平均分子量１２００００
　表１に、実施例１、２、及び比較例１～４の熱可塑性重合体組成物を構成する水添ブロック共重合体の組成、および重量平均分子量を示す。 <Isobutylene-based crosslinked polymer (a) obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal>
・ Ingredient (a)
Product name: Shibster P1140B, manufacturer name: Kaneka Co., Ltd., type: pelletized cross-linked polymer <vinyl aroma> obtained by dynamically cross-linking polypropylene and polybutene to a compound composed of an isobutylene polymer having an alkenyl group at the terminal Hydrogenated block copolymer (b) obtained by hydrogenating a block copolymer composed mainly of a polymer block composed mainly of a group compound and a polymer block composed mainly of a conjugated diene composed of isoprene and butadiene>
・ Ingredient (b-1)
Product name: Septon 4055, manufacturer name: Kuraray Co., Ltd., type: hydrogenated block copolymer of styrene-isoprene-butadiene-styrene type triblock copolymer, styrene content: 30% by mass, weight average molecular weight 270000
・ Ingredient (b-2)
Product name: Septon 4044, manufacturer name: Kuraray Co., Ltd., type: hydrogenated block copolymer of styrene-isoprene-butadiene-styrene type triblock copolymer, styrene content: 32% by mass, weight average molecular weight 170000
・ Ingredient (b-3)
Product name: Septon 4033, manufacturer name: Kuraray Co., Ltd., type: hydrogenated block copolymer of styrene-isoprene / butadiene-styrene type triblock copolymer, styrene content: 30% by mass, weight average molecular weight 90000
<Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer consisting of a polymer block mainly composed of vinyl aromatic compound and a polymer block mainly composed of conjugated diene composed of isoprene>
・ Ingredient (c-1)
Product name: Hibler 7135, manufacturer name: Kuraray Co., Ltd., type: hydrogenated block copolymer of styrene-isoprene-styrene type triblock copolymer, styrene content: 32 mass%, weight average molecular weight 280000
・ Ingredient (c-2)
Product name: Hibler 7125, manufacturer name: Kuraray Co., Ltd., type: hydrogenated block copolymer of styrene-isoprene-styrene type triblock copolymer, styrene content: 20% by mass, weight average molecular weight 120,000
Table 1 shows the compositions and weight average molecular weights of the hydrogenated block copolymers constituting the thermoplastic polymer compositions of Examples 1 and 2 and Comparative Examples 1 to 4.
＜ポリブテン（ｄ）＞
・成分（ｄ－１）
製品名：日石ポリブテンＨＶ－１００、製造会社名：ＪＸ　日鉱日石エネルギー株式会社、種類：ポリブテン、１００℃で測定した動粘度：２００ｍｍ２／ｓ <Polybutene (d)>
・ Ingredient (d-1)
Product name: Nisseki Polybutene HV-100, manufacturer: JX Nippon Oil & Energy Corporation, type: polybutene, kinematic viscosity measured at 100 ° C: 200 mm 2 / s
＜プロピレン系重合体（ｅ）＞
・成分（ｅ－１）
製品名：プライムポリプロピレン　Ｊ１０８Ｍ、製造会社名：プライムポリマー（株）、種類：ホモタイプのポリプロピレン、ＭＦＲ（２３０℃、２１Ｎ）：４５ｇ／１０ｍｉｎ <Propylene polymer (e)>
・ Ingredient (e-1)
Product Name: Prime Polypropylene J108M, Manufacturer Name: Prime Polymer Co., Ltd., Type: Homotype Polypropylene, MFR (230 ° C., 21N): 45 g / 10 min
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記の結果から、本発明で規定する、末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）、ビニル芳香族化合物を主体とする重合体ブロックとイソプレンとブタジエンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られ、特定の重量平均分子量を有する水添ブロック共重合体（ｂ）、ビニル芳香族化合物を主体とする重合体ブロックとイソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体に水素添加して得られ、特定の重量平均分子量を有する水添ブロック共重合体（ｃ）ポリブテン（ｄ）、プロピレン系重合体（ｅ）を含有する実施例１～２の熱可塑性重合体組成物は、良好なガスバリア性、流動性、耐熱性、表面特性、引張強度等の力学物性を示すことがわかる。
　これに対し、比較例１の熱可塑性重合体組成物は、水添ブロック共重合体（ｂ）の重量平均分子量が低いため表面特性、耐熱性及び引張強度に劣る。
　また、比較例２の熱可塑性重合体組成物は、水添ブロック共重合体（ｂ）および水添ブロック共重合体（ｃ）の重量平均分子量が低いため表面特性、耐熱性及び引張強度に劣る。
　さらに、比較例３の熱可塑性重合体組成物は、水添ブロック共重合体（ｂ）および水添ブロック共重合体（ｃ）を含有していないため、表面特性、流動性及び引張強度に劣る。
　さらに、比較例４の熱可塑性重合体組成物は、末端にアルケニル基を有するイソブチレン系重合体を動的架橋してなるイソブチレン系架橋熱可塑性重合体組成物（ａ）および水添ブロック共重合体（ｃ）を含有していないために、ガスバリア性、耐熱性に劣る。 From the above results, the isobutylene-based cross-linked polymer (a) obtained by cross-linking an isobutylene-based polymer having an alkenyl group at the terminal, a polymer block mainly composed of a vinyl aromatic compound, isoprene, and butadiene as defined in the present invention. A hydrogenated block copolymer (b) having a specific weight average molecular weight obtained by hydrogenation of a block copolymer comprising a polymer block mainly comprising a conjugated diene comprising a vinyl aromatic compound. Hydrogenated block copolymer (c) polybutene (d) obtained by hydrogenating a block copolymer comprising a polymer block mainly composed of a polymer block and a conjugated diene comprising isoprene and having a specific weight average molecular weight The thermoplastic polymer compositions of Examples 1 and 2 containing the propylene polymer (e) have good gas barrier properties, fluidity, heat resistance, Surface properties, mechanical properties such as tensile strength it can be seen that.
On the other hand, since the weight average molecular weight of the hydrogenated block copolymer (b) is low, the thermoplastic polymer composition of Comparative Example 1 is inferior in surface characteristics, heat resistance and tensile strength.
The thermoplastic polymer composition of Comparative Example 2 is inferior in surface properties, heat resistance and tensile strength because the weight average molecular weight of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is low. .
Furthermore, since the thermoplastic polymer composition of Comparative Example 3 does not contain the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c), it is inferior in surface characteristics, fluidity and tensile strength. .
Furthermore, the thermoplastic polymer composition of Comparative Example 4 includes an isobutylene-based crosslinked thermoplastic polymer composition (a) obtained by dynamically crosslinking an isobutylene-based polymer having an alkenyl group at the terminal, and a hydrogenated block copolymer. Since (c) is not contained, it is inferior to gas barrier property and heat resistance.
　本発明の熱可塑性重合体組成物は、ガスバリア性、流動性、耐熱性、表面特性、引張強度等の力学物性に優れているため、医療用部材、自動車、車両材料、建築材料、電気・電子製品、食品容器、日用品、その他のあらゆる分野でのパッキン材、ホース、チューブはもとより、自動車内装材、外装材、床材、家電製品部品、ＯＡ機器等の電気、電子部品、食品用器具、オーディオ機器、各種スイッチ、光ケーブル、スポーツ用品、靴、建材、玩具、文具等の幅広い用途に有効に使用することができる。
  The thermoplastic polymer composition of the present invention is excellent in mechanical properties such as gas barrier properties, fluidity, heat resistance, surface properties, and tensile strength, so that it is a medical member, automobile, vehicle material, building material, electric / electronic Products, food containers, daily necessities, packing materials, hoses, tubes in all other fields, automobile interior materials, exterior materials, flooring materials, home appliance parts, OA equipment and other electrical and electronic parts, food appliances, audio It can be effectively used in a wide range of applications such as equipment, various switches, optical cables, sports equipment, shoes, building materials, toys, and stationery.

Claims (8)

  1. 　末端にアルケニル基を有するイソブチレン系重合体を架橋してなるイソブチレン系架橋重合物（ａ）：１００質量部、
    ビニル芳香族化合物を主体とする重合体ブロックと、イソプレンとブタジエンとからなる共役ジエンを主体とする重合体ブロックとからなるブロック共重合体を水素添加して得られ、重量平均分子量が１５００００～５０００００である水添ブロック共重合体（ｂ）：１０～１００質量部、
    ビニル芳香族化合物を主体とする重合体ブロックと、イソプレンからなる共役ジエンを主体とする重合体ブロックからなるブロック共重合体を水素添加して得られ、重量平均分子量が２０００００～５０００００である水添ブロック共重合体（ｃ）：１０～１００質量部、ポリブテン（ｄ）：５～１００質量部、および
    プロピレン系重合体（ｅ）：１～１００質量部
    を含有してなる熱可塑性重合体組成物。     Isobutylene-based crosslinked polymer (a) obtained by crosslinking an isobutylene-based polymer having an alkenyl group at the terminal: 100 parts by mass
    A block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene composed of isoprene and butadiene is obtained by hydrogenation, and has a weight average molecular weight of 150,000 to 500,000. Hydrogenated block copolymer (b): 10 to 100 parts by mass
    A hydrogenated hydrogen block having a weight average molecular weight of 200,000 to 500,000, obtained by hydrogenating a polymer block mainly composed of a vinyl aromatic compound and a block copolymer composed mainly of a conjugated diene composed of isoprene. Thermoplastic polymer composition containing block copolymer (c): 10 to 100 parts by mass, polybutene (d): 5 to 100 parts by mass, and propylene polymer (e): 1 to 100 parts by mass .
  2. 　イソブチレン系架橋重合物（ａ）１００質量部に対して、水添ブロック共重合体（ｂ）と水添ブロック共重合体（ｃ）との質量の和が２０～１６０質量部である請求項１に記載の熱可塑性重合体組成物。 The sum of the masses of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is 20 to 160 parts by mass with respect to 100 parts by mass of the isobutylene-based crosslinked polymer (a). The thermoplastic polymer composition described in 1.
  3. 　前記ポリブテン（ｄ）を１００℃で測定した動粘度が１００ｍｍ２／ｓ以上である請求項１または２に記載の熱可塑性重合体組成物。 The thermoplastic polymer composition according to claim 1, wherein the polybutene (d) has a kinematic viscosity measured at 100 ° C. of 100 mm 2 / s or more.
  4. 　イソブチレン系架橋重合物（ａ）が動的架橋によって得られた重合物である請求項１～３のいずれか１項に記載の熱可塑性重合体組成物。 The thermoplastic polymer composition according to any one of claims 1 to 3, wherein the isobutylene-based crosslinked polymer (a) is a polymer obtained by dynamic crosslinking.
  5. 　請求項１～４のいずれか１項に記載の熱可塑性重合体組成物を用いたパッキン材。 A packing material using the thermoplastic polymer composition according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれか１項に記載の熱可塑性重合体組成物を用いた医療用部材。 A medical member using the thermoplastic polymer composition according to any one of claims 1 to 4.
  7. 　請求項１～４のいずれか１項に記載の熱可塑性重合体組成物を用いたチューブ。 A tube using the thermoplastic polymer composition according to any one of claims 1 to 4.
  8. 　請求項１～４のいずれか１項に記載の熱可塑性重合体組成物を用いたホース。 A hose using the thermoplastic polymer composition according to any one of claims 1 to 4.
PCT/JP2015/051952 2014-01-29 2015-01-26 Thermoplastic polymer composition having excellent gas barrier properties WO2015115346A1 (en)

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JP2016124906A (en) * 2014-12-26 2016-07-11 アロン化成株式会社 Thermoplastic elastomer composition
JP2016150980A (en) * 2015-02-18 2016-08-22 リケンテクノス株式会社 Thermoplastic elastomer resin composition
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JP2016089047A (en) * 2014-11-05 2016-05-23 Ｍｃｐｐイノベーション合同会社 Thermoplastic elastomer composition
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