JP6589180B2 - Thermoplastic polymer composition having excellent gas barrier properties - Google Patents

Description

  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. 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 pamphlet JP 2010-227285 A

  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.

  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.

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 consisting of 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,
Hydrogenation 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 and having a weight average molecular weight of 200,000 to 500,000 Block copolymer (c): 10 to 100 parts by mass, polybutene (d): 5 to 100 parts by mass, and propylene-based polymer (e): 1 to 100 parts by mass,
Is a thermoplastic polymer composition.

  The present invention also includes a packing material, a medical member, a tube, and a hose using the thermoplastic polymer composition.

  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.

  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).

<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.

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.

  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.

  Furthermore, although the thermoplastic polymer composition of the present invention is not limited in the case where the desired utility is obtained, a polybutene and a polyolefin polymer are further mixed with an 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.

<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. . Among these, styrene and α-methylstyrene are preferable. A vinyl aromatic compound may be used individually by 1 type, and may use 2 or more types together.

  The vinyl aromatic compound content in the hydrogenated block copolymer (b) is preferably 5 to 75% by mass, 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.

  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.

  50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (b) are preferably hydrogenated, 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, and the polymer block ( When B) is represented by B, it is a triblock structure represented by A-B-A, or (A-B), (A-B) _n -A, where n represents an integer of 2 or more. Among them, a triblock structure represented by A-B-A 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 important in the range of 150,000 to 500,000 from the viewpoint of molding processability and heat resistance, and 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.

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

  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. It is 10-100 mass parts with respect to a part, Preferably it is 10-80 mass parts. 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, α-methylstyrene, o, m or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. . Among these, styrene and α-methylstyrene are preferable. 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.

Contact Itewa the hydrogenated block copolymer (c), it is important to use isoprene in terms of mechanical properties and surface properties such as gas barrier properties and tensile strength.

  It is preferable that 50% or more of the carbon-carbon double bonds derived from the conjugated diene compound in the hydrogenated block copolymer (c) are hydrogenated, 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 C-D-C, or (C-D) _n , (C-D) _n -C, (where n represents an integer of 2 or more) Among them, a triblock structure represented by C—D—C is particularly preferable in terms 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.

  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. It is 10-100 mass parts with respect to it, Preferably it is 10-80 mass parts. 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.

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) to the hydrogenated block copolymer (c) is preferably in the range of 90/10 to 10/90.

<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.

  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. 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)>
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 and 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.

  It is preferable that the melt flow rate (MFR) measured on condition of 230 degreeC and 21N of a propylene polymer (e) is 5 g / 10min 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 in accordance with JIS K7210.

  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. It is 1-100 mass parts with respect to a mass part, Preferably it is 1-80 mass parts. 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.

  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 -Phenolic antioxidants such as undecane, phosphite antioxidants, thioether antioxidants, and the like can be used. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the components (a) to (e) contained in the thermoplastic polymer composition of the present invention, It is more preferable that it is 0.05-1.0 mass part.

  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.

  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. .

<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.

<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.

<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.

  The thermoplastic polymer composition of the present invention can be used as various industrial products and industrial parts regardless of the applications listed above. 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 TV, stereo, vacuum cleaner; underwater products such as underwater glasses and underwater camera covers; automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc .; 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;

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. The physical properties of the following examples and comparative examples were evaluated by the methods shown below.

(1) Hardness The thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection-molded at 230 ° C. to form a sheet having a thickness of 2 mm, and JIS-A hardness was measured according to 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. 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 characteristics By tracing the injection-molded sheets of the thermoplastic polymer compositions obtained in Examples and Comparative Examples with a fingertip, it was used as an index of surface properties (no stickiness: ○, little stickiness: Δ, stickiness) Yes: x).

<Examples 1-2 and Comparative Examples 1-4>
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.).

<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, manufacturing company name: Kaneka Co., Ltd., type: pelletized cross-linked polymer <vinyl aroma> obtained by dynamically cross-linking polypropylene and polybutene to a compound comprising 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>
-Component (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 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>
-Component (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
-Component (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
In Table 1, the composition of the hydrogenated block copolymer which comprises the thermoplastic polymer composition of Examples 1, 2 and Comparative Examples 1-4, and a weight average molecular weight are shown.

<Polybutene (d)>
-Component (d-1)
Product name: Nisseki Polybutene HV-100, Manufacturer name: JX Nippon Oil & Energy Corporation, Type: Polybutene, Kinematic viscosity measured at 100 ° C .: 200 mm ² / s

<Propylene polymer (e)>
-Component (e-1)
Product Name: Prime Polypropylene J108M, Manufacturer Name: Prime Polymer Co., Ltd., Type: Homotype Polypropylene, MFR (230 ° C., 21N): 45 g / 10 min

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.

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)

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 consisting of 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,
The block copolymer comprising a polymer block consisting of polymer block and isoprene mainly of a vinyl aromatic polymer obtained by hydrogenating, hydrogenated block copolymer weight average molecular weight of 200 thousand to 500 thousand (c ): 10 to 100 parts by mass, polybutene (d): 5 to 100 parts by mass, and propylene polymer (e): a thermoplastic polymer composition comprising 10 to 100 parts by mass.   The sum of the masses of the hydrogenated block copolymer (b) and the hydrogenated block copolymer (c) is from 20 to 160 parts by mass per 100 parts by mass of the isobutylene-based crosslinked polymer (a). The thermoplastic polymer composition described in 1. 3. 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.   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.   The packing material using the thermoplastic polymer composition of any one of Claims 1-4.   The medical member using the thermoplastic polymer composition of any one of Claims 1-4.   The tube using the thermoplastic polymer composition of any one of Claims 1-4.   The hose using the thermoplastic polymer composition of any one of Claims 1-4.