JP5251347B2 - Thermoplastic elastomer composition, method for producing the same, and pneumatic tire using the same - Google Patents

Thermoplastic elastomer composition, method for producing the same, and pneumatic tire using the same Download PDF

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JP5251347B2
JP5251347B2 JP2008204693A JP2008204693A JP5251347B2 JP 5251347 B2 JP5251347 B2 JP 5251347B2 JP 2008204693 A JP2008204693 A JP 2008204693A JP 2008204693 A JP2008204693 A JP 2008204693A JP 5251347 B2 JP5251347 B2 JP 5251347B2
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直之 師岡
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横浜ゴム株式会社
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  The present invention relates to a thermoplastic elastomer composition, a method for producing the same, and a pneumatic tire using the same, and more particularly, a thermoplastic elastomer composition that retains high gas barrier properties even when repeatedly deformed and has excellent melt processability. In addition, the present invention relates to a manufacturing method thereof and a pneumatic tire using the same.

  Conventionally, a rubber composition mainly composed of butyl rubber, halogenated butyl rubber or the like is used for an inner liner disposed as an air barrier layer on the inner surface of the tire in order to maintain the internal pressure of the tire. However, since these rubber compositions mainly composed of butyl rubber have low air barrier properties, when such rubber composition is used for an inner liner, the thickness of the inner liner needs to be about 1 mm to 4 mm. The weight of the inner liner in the tire is about 5%, which is an obstacle to reducing the weight of the tire and improving the fuel efficiency of the automobile.

  On the other hand, ethylene-vinyl alcohol copolymer (EVOH) is known to be excellent in gas barrier properties, and the air permeation amount is 1/100 or less of the rubber composition for an inner liner of the butyl rubber. Even with a thickness of 100 μm or less, the internal pressure retention performance of the tire can be greatly improved, and the weight of the tire can be reduced. For example, Patent Literature 1 and Patent Literature 2 disclose a pneumatic tire including an inner liner made of EVOH. However, when normal EVOH is used as the inner liner, the effect of improving the internal pressure retention performance of the tire is great, but normal EVOH has a significantly higher elastic modulus than rubber normally used in tires, so tire running Sometimes, when subjected to repeated bending and tensile deformation, the EVOH layer is fatigued, and there is a problem that the internal pressure holding performance after use of the tire is significantly reduced as compared with the internal pressure holding performance before use of the tire. As means for solving this problem, Patent Document 3 discloses that an ethylene content of 20 to 70 mol%, an ethylene-vinyl alcohol copolymer having a saponification degree of 85% or more, 60 to 99 wt%, and a hydrophobic plasticizer 1 to 40 are used. A technique of using a resin composition consisting of% by weight for an inner liner is disclosed. Further, Patent Document 4 describes a modified ethylene-vinyl alcohol copolymer obtained by reacting 1 to 50 parts by weight of an epoxy compound with 100 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 25 to 50 mol%. A technique for using a coalescence for an inner liner is disclosed. Patent Document 5 discloses a resin composition in which a soft resin having a Young's modulus at 23 ° C. smaller than that of the modified ethylene-vinyl alcohol copolymer is dispersed in a matrix composed of the epoxy compound-modified ethylene-vinyl alcohol copolymer. A technique using an inner liner for a tire including a phase composed of a product is disclosed. However, even with the technique disclosed above, the internal pressure retention performance after running of the tire still deteriorated, and there was a need for improvement.

  Patent Document 6 discloses a composition in which a modified polymer such as a polyamide resin and an ethylene-unsaturated carboxylic acid copolymer is blended as a method for improving the impact resistance and durability of a vinyl alcohol resin. Yes. However, since the polyamide resin and the ethylene-unsaturated carboxylic acid copolymer in the composition react during the melt mixing, the composition obtained can be increased by increasing the filling amount of the modified polymer into the thermoplastic resin. There was a problem that the melt viscosity of the resin became extremely high, and the extrusion processability deteriorated remarkably. In addition, by reducing the melt viscosity of the polyamide resin that is the matrix phase, the melt viscosity of the resulting composition can also be reduced. However, this method deteriorates the dispersibility of the modified polymer and deteriorates the durability. There was a problem of letting it go, and there was room for further improvement.

JP-A-1-314164 JP-A-6-40207 JP 2002-52904 A JP 2004-176048 A JP 2008-24217 A JP 2003-277564 A

  Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition excellent in gas barrier property / melt processability / fatigue resistance, and further, for a pneumatic tire that suppresses a decrease in internal pressure retention performance after running the tire. It is to provide an inner liner.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) 20 to 80 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene composition ratio of 20 to 50 mol% and a saponification degree of 90% or more, (B) 80 to 20 parts by weight of a layered silicate-modified polyamide resin prepared by an interlayer polymerization method, (C) 10 to 50 parts by weight of the hydrophobic plasticizer with respect to 100 parts by weight of the total amount of components (A) and (B). The modified polymer having parts by weight and (D) acid anhydride group comprises 60 to 150 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B), and component (D) is component A thermoplastic elastomer composition that forms a dispersed phase dispersed in a matrix phase of (A), (B), and (C), a method for producing the same, and a pneumatic tire using the same are provided.

  According to the present invention, as a polyamide resin blended with EVOH (A), a layered silicate-modified polyamide resin (B) prepared by an interlayer polymerization method is used, which contains a hydrophobic plasticizer (C), and an acid. By blending the modified polymer (D) having an anhydride group, the component (D) is dispersed as a dispersed phase in the matrix phase of the components (A), (B), and (C), and the amount of filling of the dispersed phase is increased. The increase in melt viscosity can be suppressed while increasing, and as a result, a thermoplastic elastomer composition excellent in gas barrier property / fatigue resistance / melt processability can be obtained.

  As a result of researches to achieve the above-mentioned object, the inventors of the present invention blended EVOH with excellent gas barrier properties and polyamide resin with excellent fatigue resistance. Thermoplastic elastomer excellent in gas barrier property / fatigue resistance / melt processability by melt-mixing a modified polymer having a hydrophobic plasticizer and an acid anhydride group using the layered silicate modified polyamide resin Succeeded in obtaining the composition.

  According to the present invention, (A) an ethylene-vinyl alcohol copolymer (EVOH) having an ethylene composition ratio of 20 to 50 mol%, preferably 35 to 50 mol%, and a saponification degree of 90% or more, preferably 99% or more. 20 to 80 parts by weight, preferably 40 to 70 parts by weight, (B) 80 to 20 parts by weight, preferably 60 to 30 parts by weight (layers (A) and (B ) Total amount: 100 parts by weight), (C) the hydrophobic plasticizer is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). And (D) the modified polymer having an acid anhydride group comprises 60 to 150 parts by weight, preferably 70 to 100 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B), The dispersed phase of component (D) is component ( ), It can be obtained (B) and a thermoplastic elastomer composition dispersed in a matrix phase of (C).

  The hydrophobic plasticizer (C) used in the present invention is not particularly problematic as long as the solubility parameter (SP value) calculated from the Fedors equation is in the range of 9 to 15, for example, aromatic ester, aliphatic ester, phosphoric acid. Any known hydrophobic plasticizer such as ester or sulfonamide plasticizer can be used, and in particular, sulfonamide plasticizer (for example, butylbenzenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluene) Use of sulfonamide, N-cyclohexyl-p-toluenesulfonamide) and the like is preferable from the viewpoint of compatibility with the polyamide resin used in the present invention. When the amount of the hydrophobic plasticizer (C) used is small, the reaction between the acid anhydride group of the modified polymer and the polyamide resin proceeds during melt mixing, and the melt viscosity of the resulting thermoplastic elastomer composition is extremely high. Therefore, the processability is deteriorated, which is not preferable. On the other hand, when the content is large, the hydrophobic plasticizer bleeds out to the surface of the thermoplastic elastomer composition and the handling is deteriorated.

  The polyamide resin in the layered silicate-modified polyamide resin used as component (B) in the present invention includes nylon 6.66, nylon 6.12, nylon containing 90 mol% or more of nylon 6 and / or ε-caprolactam-derived component. 6.66.12, nylon 6.10 and the like can be used alone or as an arbitrary mixture. As said polyamide resin (B), the layered silicate modified polyamide resin which can be produced with the following method can be used.

The modified polyamide resin is used in an amount of 80 to 20 parts by weight (both in total 100 parts by weight) with respect to 20 to 80 parts by weight of EVOH, preferably 60 to 30 parts by weight with respect to 40 to 70 parts by weight of EVOH. The layered silicate-modified polyamide resin used in the present invention is produced by uniformly dispersing and combining 0.1 to 10% by weight, preferably 1 to 4% by weight of a layered silicate with respect to the unmodified polyamide resin. . Regarding the method of dispersing the layered silicate in the polyamide, a swelling agent (for example, ammonium salt of ω-amino acid having molecular formula: H 2 N— (CH 2 ) n-1 COOH) and metal ions in the layered silicate May be ion-exchanged, the interlayer is expanded, and a monomer is further taken in and polymerized (interlayer polymerization method). The layered silicate for modifying the polyamide resin is a layered clay mineral, and is not particularly limited as such a layered clay mineral. Kaolinite such as halosite: Vermiculite such as dioctahedral vermiculite and trioctahedral vermiculite: Mio such as teniolite, tetralithic mica, mascobite, illite, sericite, phologbite, biotite, etc. Although used, it is particularly preferable to use montmorillonite having a strong interaction force with the polyamide resin. As the polyamide resin, at least one of nylon 6 and nylon 6.66 is preferable from the viewpoint of excellent balance between compatibility with EVOH and fatigue resistance.

  As the modified polymer (D) used in the present invention, for example, a soft polymer such as an ethylene-α olefin copolymer graft-modified with an acid anhydride group is preferably used, and the modified polymer having such an acid anhydride group is used. The polymer (D) is known, for example, maleic anhydride modified ethylene-propylene copolymer (Tuffmer MP-0620), maleic anhydride modified ethylene-butene copolymer (Tuffmer MP-7020) manufactured by Mitsui Chemicals, Inc. In the present invention, such a processed commercial product can be used.

  The thermoplastic elastomer composition according to the present invention is obtained by, for example, melt-mixing the layered silicate-modified polyamide resin (B) and the hydrophobic plasticizer (C) in advance at a temperature of, for example, 20 ° C. plus the melting point of the polyamide resin. Then, EVOH (A) and modified polymer (D) can be produced by melt mixing.

  The thermoplastic elastomer composition according to the present invention can be formed into a film by an extruder with a T-die or an inflation molding machine, and this film is excellent in gas barrier properties, heat resistance, and bending fatigue resistance. It can be suitably used as an inner liner of a pneumatic tire.

  According to the present invention, in producing the inner liner, a thermoplastic elastomer laminate in which rubber composition layers are laminated on both surfaces of the thermoplastic elastomer composition film is used as a tire innermost layer inner liner of a pneumatic tire. It is preferable to use as. When a tire is produced using this laminate, the maximum temperature of the laminate during vulcanization is not less than the melting point of EVOH (A) and lower than the melting point of aliphatic polyamide (B), and further a plasticizer is adjacent to the rubber. By shifting to the composition layer and reducing the amount of plasticizer remaining in the thermoplastic resin composition to 3 parts by weight or less, the orientation of EVOH (A) in the vulcanization process can be suppressed, and the air pressure is maintained after running the tire. Performance can be maintained.

  In addition to the components described above, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, and anti-aging agents. Various additives generally blended for resins and rubber compositions such as these can be blended, and these additives are kneaded by a general method into a composition and used for vulcanization or crosslinking can do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

(1) Production method of thermoplastic elastomer composition In the raw materials shown in Table I and the formulation shown in Table II, a thermoplastic resin composition and a thermoplastic elastomer composition were produced by the following methods.

Reference Examples 1-3
In advance, BM-4, which is a hydrophobic plasticizer, and a polyamide resin (or a layered silicate-modified polyamide resin) are mixed with a biaxial kneader (TEX44 manufactured by Nippon Steel Works, hereinafter, all using this biaxial kneader). The mixture was melt-kneaded under a kneader temperature of 230 ° C. to prepare a hydrophobic plasticizer / polyamide resin (or layered silicate-modified polyamide resin) blend. Next, an ethylene-vinyl alcohol copolymer and a hydrophobic plasticizer / polyamide resin (or layered silicate-modified polyamide resin) are melt-kneaded using a twin-screw kneader at a kneader temperature of 220 ° C. to obtain thermoplasticity. Resin composition pellets were prepared.

Comparative Examples 1-7 and Examples 1-7
A hydrophobic plasticizer is prepared by melt-kneading BM-4, which is a hydrophobic plasticizer, and a polyamide resin (or a layered silicate-modified polyamide resin) in a biaxial kneader at a kneader temperature of 230 ° C. in advance. / A polyamide resin (or layered silicate-modified polyamide resin) blend was prepared. Next, ethylene-vinyl alcohol copolymer, hydrophobic plasticizer / polyamide resin (or layered silicate-modified polyamide resin) and modified polymer MP-0620 (Tafmer MP-0620 manufactured by Mitsui Chemicals, Inc.) modified with maleic anhydride Ethylene propylene copolymer) was melt-kneaded using a twin-screw kneader at a kneader temperature of 220 ° C. to produce thermoplastic elastomer composition pellets.

Example 8
Thermoplastic elastomer composition pellets obtained by melt-kneading ethylene-vinyl alcohol copolymer, layered silicate-modified polyamide resin, BM-4, and MP-0620 in a twin-screw kneader at a kneading temperature of 220 ° C. Was made.

(2) Melt viscosity η PA measurement method of raw material polyamide resin The melt viscosity η PA of the raw material polyamide resin at 250 ° C. and a shear rate of 122 sec −1 was measured using a capillary rheometer manufactured by Toyo Seiki Co., Ltd.

(3) Melt viscosity η TPE measurement method of thermoplastic elastomer composition Using a capillary rheometer manufactured by Toyo Seiki Co., Ltd., the melt viscosity η TPE of the thermoplastic elastomer composition pellets at 250 ° C and shear rate 122 sec -1 It was measured.

(4) Method for measuring dispersed particle size of modified polymer (D) The thermoplastic elastomer composition pellets of Comparative Examples 1 to 7 and Examples 1 to 8 were frozen at a temperature of −100 ° C., and the sample was cut with a microtome. After the fresh surface was taken out, the number average dispersed particle size of the modified polymer (D) was measured by observing the surface with an atomic force microscope (SP-300HV, manufactured by SII Nanotechnology).

(5) Production method of thermoplastic elastomer composition film Using a single-screw extruder with a 550 mm wide T-type die, the following Extrusion conditions, Reference Examples 1 to 3, Comparative Examples 1 to 7 and Examples 1 to 8 The illustrated thermoplastic resin composition and thermoplastic elastomer composition pellets were formed into a film having an average thickness of 20 μm.

Extruder: φ40mm single screw extruder (Pura Giken Co., Ltd.)
Extrusion temperature: C1 / C2 / C3 / C4 / die = 200/210/230/235/235 ° C.
Cooling roll temperature: 50 ° C
Pickup speed: 4m / min

(6) Manufacturing method of rubber composition In the raw materials and blends shown in Table III, when ingredients other than the vulcanization accelerator and the vulcanizing agent were kneaded for 5 minutes with a 16 liter closed mixer and reached 140 ° C A master batch was obtained by discharge. A vulcanization accelerator and a vulcanizing agent were kneaded with this master batch using an open roll to obtain a rubber composition. The rubber composition 1 was rolled and molded to a width of 500 mm / 300 μm, and the rubber composition 2 was rolled and molded to a width of 500 mm and a thickness of 1000 μm to obtain an unvulcanized rubber composition sheet.

  Using the thermoplastic resin composition, the plastic elastomer composition film, and the unvulcanized rubber composition sheet obtained as described above, a pneumatic tire is produced by the following method and evaluated by the following method. went.

(1) Test Tire Manufacturing Method A rubber composition 1 sheet was laminated on both surfaces of a thermoplastic resin composition film or a thermoplastic elastomer composition film, and this was used as an inner liner for a tire. Subsequently, a pneumatic tire for passenger cars of 195 / 65R15 arranged so that the laminate was the innermost surface was produced according to a conventional method under conditions of a vulcanization temperature of 178 ° C. and a vulcanization time of 12 minutes.

(2) Air pressure retention performance index before driving After mounting the test tire produced by the above method on a 6JJ × 15 rim, it was evaluated by filling the internal pressure with 240 kPa and measuring the internal pressure after 3 months. Turned into.
Pre-travel air pressure holding performance = [(240−b)] / (240−a)] × 100
here,
a: Internal pressure (kPa) after 3 months of a non-running tire using two rubber composition sheets as an inner liner
b: Internal pressure (kPa) after 3 months of tire before running

(3) Post-travel air pressure retention performance index The test tire produced by the above method was pressed at a load of 6 kN onto a drum having an internal pressure of 190 kPa and a rotational speed corresponding to 80 km / h, and traveled for 10,000 km. Next, after this running tire was mounted on a 6JJ × 15 rim, it was evaluated by filling the internal pressure with 240 kPa and measuring the internal pressure after 3 months, and indexed by the following formula.
Air pressure holding performance after running = [(240−b)] / (240−a)] × 100
here,
a: Internal pressure (kPa) after 3 months of a non-running tire using two rubber composition sheets as an inner liner
b: Internal pressure (kPa) after 3 months of running tire

(4) Air pressure retention performance maintenance ratio The air pressure retention performance maintenance ratio was defined by the following equation.
Air pressure retention performance maintenance rate (%)
= (Air pressure retention performance index after traveling / air pressure retention performance index before traveling) × 100

Table I footnotes
Ethylene-vinyl alcohol copolymer resin (A)
H171B: Ethylene composition ratio 38 mol% ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd.)
Polyamide resin (B)
1022C2: 2% by weight montmorillonite-modified nylon 6 (manufactured by Ube Industries)
5034C2: 2% by weight montmorillonite modified nylon 6.66 (manufactured by Ube Industries)
1022B: Nylon 6 (manufactured by Ube Industries, Ltd., high viscosity type)
1013B: Nylon 6 (Ube Industries, Ltd., low viscosity type)
Hydrophobic plasticizer (C)
BM-4: N-butylbenzenesulfonamide (manufactured by Daihachi Chemical Industry Co., Ltd.)
Acid anhydride modified polymer (D)
MP-0620: Maleic anhydride modified ethylene-propylene copolymer (manufactured by Mitsui Chemicals, Inc.)

  The thermoplastic resin compositions shown in Reference Examples 1 to 3 have low melt viscosity and excellent extrudability. However, when this is used for an inner liner of a pneumatic tire, the air pressure retention performance before running is excellent. The air pressure holding performance after running was greatly reduced, and the air pressure holding performance could not be maintained.

  Since the thermoplastic elastomer composition shown in Comparative Example 1 uses an unmodified polyamide resin and has a large amount of the modified polymer, the resulting thermoplastic elastomer composition has an extremely high melt viscosity, and is formed into a film by melt molding. I could not.

  The thermoplastic elastomer composition shown in Comparative Example 2 has a low melt viscosity and excellent extrudability, but is inferior in durability because the blending amount of the modified polymer (D) does not satisfy the specified amount, and is a pneumatic tire. When used in the inner liner, the air pressure holding performance before running was excellent, but the air pressure holding performance after running was greatly reduced, and the air pressure holding performance could not be maintained.

  In Comparative Examples 3 and 4, since an unmodified polyamide resin having a low melt viscosity was used, the resulting thermoplastic elastomer composition had a low melt viscosity and could be formed into a film, but the modified polymer dispersibility deteriorated. did. For this reason, although the air pressure retention performance before traveling is excellent, the air pressure retention performance after traveling is significantly lowered, and the air pressure retention performance cannot be maintained.

  Comparative Example 5 uses a layered silicate-modified polyamide resin, but the thermoplastic elastomer composition obtained because the amount of the hydrophobic plasticizer (C) is small and the amount of the modified polymer (D) is large. The melt viscosity of the film became extremely high and could not be formed into a film by melt molding.

  Since Examples 1-7 use the layered silicate-modified polyamide resin, the melting of the thermoplastic elastomer composition does not deteriorate the dispersibility of the modified polymer (D) as in Comparative Examples 3 and 4. Viscosity can be reduced, and filming is also possible. A pneumatic tire using this film as an inner liner had high air pressure retention performance before and after running and had excellent performance.

  According to the present invention, a layered silicate-modified polyamide resin (B) prepared by an interlayer polymerization method, particularly with a polyamide resin, together with a hydrophobic plasticizer (C), by combining the specific components (A) to (D). As a result, the dispersion phase of the modified polymer (D) modified with an acid anhydride can be highly charged with good dispersibility in the resin matrix, and the increase in melt viscosity can be suppressed. Thus, a thermoplastic elastomer composition excellent in gas barrier property / fatigue resistance / melt processability can be obtained, and this thermoplastic elastomer composition is useful, for example, as a composition for an inner liner of a pneumatic tire.

Claims (7)

  1. (A) 20-80 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene composition ratio of 20-50 mol% and a saponification degree of 90% or more, (B) 80-20 parts by weight of a layered silicate-modified polyamide resin, (C) An ethylene-α olefin copolymer graft-modified with 10 to 50 parts by weight and (D) an acid anhydride group with respect to 100 parts by weight of the total amount of components (A) and (B). The modified polymer containing 60 to 150 parts by weight with respect to 100 parts by weight of the total amount of component (A) and component (B), and component (D) is component (A), (B) and (C) A thermoplastic elastomer composition which forms a dispersed phase dispersed in a matrix phase.
  2.   The thermoplastic elastomer composition according to claim 1, wherein the plasticizer of component (C) is a sulfonamide plasticizer.
  3.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the layered silicate is montmorillonite.
  4.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the polyamide resin of component (B) is polyamide 6 and / or polyamide 6.66.
  5. The layered silicate-modified polyamide resin of component (B) and the hydrophobic plasticizer of component (C) are previously melt mixed, and then the ethylene-vinyl alcohol copolymer of component (A) and the modified polymer of component (D) are mixed. It melt-mixes, The manufacturing method of the thermoplastic-elastomer composition of any one of Claims 1-4 characterized by the above-mentioned.
  6. A pneumatic tire using the thermoplastic elastomer composition film according to any one of claims 1 to 4 as an inner liner.
  7. A pneumatic tire using a thermoplastic elastomer laminate in which a rubber composition layer is laminated on both surfaces of a film of the thermoplastic elastomer composition according to any one of claims 1 to 4 , as an innermost liner of a tire innermost layer. .
JP2008204693A 2008-08-07 2008-08-07 Thermoplastic elastomer composition, method for producing the same, and pneumatic tire using the same Active JP5251347B2 (en)

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JP5707728B2 (en) * 2010-04-26 2015-04-30 横浜ゴム株式会社 Thermoplastic resin composition
JP5844173B2 (en) * 2012-02-14 2016-01-13 株式会社ブリヂストン tire
EP2815894B1 (en) * 2012-02-14 2016-10-05 Bridgestone Corporation Tire
JP2016035067A (en) * 2015-10-02 2016-03-17 株式会社ブリヂストン tire

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JP4197784B2 (en) * 1998-11-24 2008-12-17 横浜ゴム株式会社 Thermoplastic elastomer composition excellent in gas barrier properties and laminates using it
JP4008143B2 (en) * 1999-03-18 2007-11-14 株式会社クラレ Multilayer structure and thermoformed containers for thermoforming
JP4942253B2 (en) * 2000-04-11 2012-05-30 横浜ゴム株式会社 Thermoplastic elastomer composition with improved processability and tire using the same
JP2002052904A (en) * 2000-08-11 2002-02-19 Kuraray Co Ltd Inner liner for tire inner face
JP2002146135A (en) * 2000-11-15 2002-05-22 Nippon Synthetic Chem Ind Co Ltd:The Resin composition
KR100508907B1 (en) * 2001-12-27 2005-08-17 주식회사 엘지화학 Nanocomposite blend composition having super barrier property
WO2007083785A1 (en) * 2006-01-17 2007-07-26 The Yokohama Rubber Co., Ltd. Low-permeable rubber laminate and pneumatic tire using same
WO2007100157A1 (en) * 2006-03-03 2007-09-07 The Yokohama Rubber Co., Ltd. Elastomer composition, method for producing same, and pneumatic tire using same
JP2008069190A (en) * 2006-09-12 2008-03-27 Ube Ind Ltd High-rigidity and low-temperature impact-resistant polyamide resin composition

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