JP2005213326A - Thermoplastic elastomer composition - Google Patents
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本発明は熱可塑性樹脂とゴムとから成る熱可塑性エラストマー組成物に関し、更に詳しくは熱可塑性樹脂を連続相、ゴムを分散層としたときのゴムの最大体積率（即ち、ゴム充填率が最大になる体積率）を増大させた熱可塑性エラストマー組成物に関する。 The present invention relates to a thermoplastic elastomer composition comprising a thermoplastic resin and rubber. More specifically, the present invention relates to a maximum volume ratio of rubber when the thermoplastic resin is a continuous phase and rubber is a dispersed layer (that is, the rubber filling ratio is maximized). The volume ratio of the thermoplastic elastomer is increased.
特許文献１は分散ゴムの微細化に関し、この文献には混練時のゴム／樹脂粘度比を０．８〜１．２にすることにより微細分散でき、またステップ混合することで粘度比を維持したままゴム量を増やすことができることを記載している。 Patent Document 1 relates to the refinement of dispersed rubber. In this document, fine dispersion can be achieved by setting the rubber / resin viscosity ratio during kneading to 0.8 to 1.2, and the viscosity ratio is maintained by step-mixing. It describes that the amount of rubber can be increased.
ゴム／熱可塑性樹脂ブレンド型熱可塑性エラストマー組成物において、ゴム体積率と弾性率、セット性に相関があることはよく知られている。ゴムをより多く配合することによって弾性率の低減、セット性の向上が可能であるが、ゴムの最大体積率はゴム／樹脂粘度比に依存するところが大きく、式：
φｄ／φｍ×ηｍ／ηｄ＜１ （Ｉ）
（式中φｄ；ゴム体積率、φｍ；樹脂体積率、ηｄ；ゴム粘度、ηｍ；樹脂粘度を示す）を満たす必要がある。また、ゴム粒径にはゴム／樹脂粘度比以外に相溶性の影響も大きく、種々の相溶化剤、相溶化手法によって相溶性の悪いゴム／樹脂の組合せでも微細ゴム分散を得られることが知られている。
In rubber / thermoplastic resin blend type thermoplastic elastomer compositions, it is well known that there is a correlation between rubber volume fraction, elastic modulus, and setability. It is possible to reduce the elastic modulus and improve the setability by blending more rubber, but the maximum volume ratio of rubber largely depends on the rubber / resin viscosity ratio.
φd / φm × ηm / ηd <1 (I)
(Where φd: rubber volume fraction, φm: resin volume fraction, ηd: rubber viscosity, ηm: resin viscosity) must be satisfied. In addition to the rubber / resin viscosity ratio, the rubber particle size is greatly affected by compatibility, and it is known that a fine rubber dispersion can be obtained even with a combination of rubber / resin having poor compatibility by various compatibilizers and compatibilization methods. It has been.
一方、充填率は粒径が一定であれば最大量も一定であるが、大小サイズの異なるサイズの粒径を混ぜ合わせれば最大量は大きくなる。通常、分散ゴムの粒径にはばらつきがあり、均一分散を得るための方法は提案されているが、大小粒径の異なるモルフォロジーを作る方法は知られていない。 On the other hand, if the particle size is constant, the maximum amount is constant, but if the particle sizes of different sizes are mixed, the maximum amount increases. Usually, there are variations in the particle diameter of the dispersed rubber, and a method for obtaining uniform dispersion has been proposed, but a method for producing morphologies with different large and small particle diameters is not known.
従って、本発明の目的は、熱可塑性エラストマー組成物中のゴムの最大体積率を増大させることにある。 Accordingly, an object of the present invention is to increase the maximum volume fraction of rubber in a thermoplastic elastomer composition.
本発明に従えば、熱可塑性樹脂（Ａ）と、熱可塑性樹脂（Ａ）と非相溶で熱可塑性樹脂（Ａ）と反応性の官能基を有さないゴム（Ｂ）に、熱可塑性樹脂（Ａ）及びゴム（Ｂ）と反応性の添加剤（Ｃ）を添加混合して得られる、熱可塑性樹脂（Ａ）が連続相、ゴム（Ｂ）が分散相である熱可塑性エラストマー組成物（Ｄ）に、熱可塑性樹脂（Ａ）と反応性の官能基を有する変性ゴム（Ｅ）を添加して得られる熱可塑性樹脂（Ａ）の連続相中にゴム（Ｂ）及び変性ゴム（Ｅ）が分散した熱可塑性エラストマー組成物が提供される。 According to the present invention, the thermoplastic resin (A) and the rubber (B) which is incompatible with the thermoplastic resin (A) and does not have a functional group reactive with the thermoplastic resin (A) are converted into the thermoplastic resin. A thermoplastic elastomer composition (A) and a rubber (B) and a reactive additive (C) are added and mixed, and the thermoplastic resin (A) is a continuous phase and the rubber (B) is a dispersed phase ( The rubber (B) and the modified rubber (E) in the continuous phase of the thermoplastic resin (A) obtained by adding the modified rubber (E) having a functional group reactive with the thermoplastic resin (A) to D) A thermoplastic elastomer composition in which is dispersed is provided.
本発明によれば、大粒径のゴム分散を得る配合工程（第１工程）と、小粒径のゴム分散を得る配合工程（第２工程）を分け、第１工程→第２工程の順に混合することによって高ゴム体積率の熱可塑性エラストマー組成物を安定して製造することができる。 According to the present invention, the blending step (first step) for obtaining rubber dispersion with a large particle size is separated from the blending step (second step) for obtaining rubber dispersion with a small particle size. By mixing, a thermoplastic elastomer composition having a high rubber volume ratio can be stably produced.
本明細書において熱可塑性樹脂（Ａ）とゴム（Ｂ）とが「非相溶」であるというのは両Ｓｐ値の差が５Ｊ1/2 ／cm3/2 以上であることをいう。 In this specification, that the thermoplastic resin (A) and the rubber (B) are “incompatible” means that the difference between the two Sp values is 5 J 1/2 / cm 3/2 or more.
本発明によれば、サイズの異なるゴム粒子の分散を意図的に作り出し、高ゴム体積率の熱可塑性エラストマー組成物を安定して製造する配合及び製造方法である。このためには、混合を２段階に分け、第１段ではゴム粒径が大きくなる配合で混合し、第２段ではゴム粒径が小さくなる配合で混合することによって、大小ゴム粒径の混在したモルフォロジーを得ることができ、高ゴム体積率の熱可塑性エラストマー組成物を安定して得ることに成功した。 According to the present invention, there is a compounding and manufacturing method for intentionally creating dispersion of rubber particles having different sizes and stably producing a thermoplastic elastomer composition having a high rubber volume fraction. For this purpose, the mixing is divided into two stages. In the first stage, the mixture is mixed with a composition that increases the rubber particle diameter, and in the second stage, the mixture is mixed with a composition that decreases the rubber particle diameter. And succeeded in stably obtaining a thermoplastic elastomer composition having a high rubber volume fraction.
ゴム粒子径の大きな熱可塑性エラストマー組成物は、熱可塑性樹脂（Ａ）との相溶性が悪いゴム（Ｂ）に、相溶化剤となる添加剤（Ｃ）を加えることによって得ることができ、ゴム粒径の小さな熱可塑性エラストマー組成物は、樹脂（Ａ）と反応して相溶性が向上する変性ゴム（Ｅ）を混合することによって得ることができる。 A thermoplastic elastomer composition having a large rubber particle diameter can be obtained by adding an additive (C) as a compatibilizer to a rubber (B) having poor compatibility with the thermoplastic resin (A). A thermoplastic elastomer composition having a small particle size can be obtained by mixing a modified rubber (E) that reacts with the resin (A) to improve compatibility.
本発明において使用することができる熱可塑性樹脂（Ａ）としては、例えば水酸基、カルボキシル基、アミノ基、アミド基、シリル基、エステル基などの官能基を有するもの、具体的にはポリアミド、ポリエステル、ポリビニルアルコール、エチレンビニルアルコール、アクリロニトリルブタジエンスチレンなどをあげることができる。これらは単独又は任意の混合物として使用することができる。 Examples of the thermoplastic resin (A) that can be used in the present invention include those having a functional group such as a hydroxyl group, a carboxyl group, an amino group, an amide group, a silyl group, and an ester group, specifically, polyamides, polyesters, Examples thereof include polyvinyl alcohol, ethylene vinyl alcohol, acrylonitrile butadiene styrene, and the like. These can be used alone or in any mixture.
本発明において使用する熱可塑性樹脂（Ａ）と非相溶性で樹脂（Ａ）と反応性の官能基を有さないゴム（Ｂ）としては、例えばポリイソブチレン−ポリイソプレン共重合体ゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレンブタジエン共重合体ゴム、天然ゴム、イソプレンゴム、ブタジエンゴムなどをあげることができ、これらの中でポリイソブチレン−ポリイソプレン共重合体ゴム、エチレン−プロピレン−ジエン共重合体ゴム、アクリロニトリル−ブタジエン共重合体ゴムの使用が好ましい。これらのゴム（Ｂ）は単独又は任意の混合物として使用することができる。ゴム（Ｂ）の使用量には特に限定はないが、樹脂（Ａ）１００重量部に対し１０〜４００重量部であるのが好ましく、５０〜２５０重量部が更に好ましい。 Examples of the rubber (B) that is incompatible with the thermoplastic resin (A) used in the present invention and does not have a functional group reactive with the resin (A) include, for example, polyisobutylene-polyisoprene copolymer rubber, ethylene- Examples thereof include propylene-diene copolymer rubber, styrene butadiene copolymer rubber, natural rubber, isoprene rubber, butadiene rubber, and the like. Among these, polyisobutylene-polyisoprene copolymer rubber, ethylene-propylene-diene copolymer The use of polymer rubber and acrylonitrile-butadiene copolymer rubber is preferred. These rubbers (B) can be used alone or as an arbitrary mixture. The amount of rubber (B) used is not particularly limited, but is preferably 10 to 400 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of resin (A).
本発明において使用する添加剤（Ｃ）は前記熱可塑性樹脂（Ａ）及びゴム（Ｂ）と反応性があるものでなければならず、例えばメチロール基、イソシアネート基、エポキシ基、チオール基、アミノ基、無水マレイン酸基などを含む低分子量化合物、アルキルフェノール樹脂のハロゲン化物などをあげることができ、特にアルキルフェノール−ホルムアルデヒト樹脂、ポリメチロールフェノール樹脂、ｍ−フェニレンビスマレイミド樹脂又はそのハロゲン化物の使用が好ましい。これらの添加剤（Ｃ）は単独又は任意の混合物として使用することができる。添加剤（Ｃ）の使用量には特に限定はないが、ゴム（Ｂ）１００重量部当り０．１〜５０重量部であるのが好ましく、１〜２０重量部であるのが更に好ましい。 The additive (C) used in the present invention must be reactive with the thermoplastic resin (A) and the rubber (B), for example, methylol group, isocyanate group, epoxy group, thiol group, amino group. And low molecular weight compounds containing a maleic anhydride group, halides of alkylphenol resins, and the like. Particularly preferred are alkylphenol-formaldehyde resins, polymethylolphenol resins, m-phenylenebismaleimide resins or their halides. These additives (C) can be used alone or as an arbitrary mixture. The amount of the additive (C) used is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the rubber (B).
本発明に従えば、前記樹脂（Ａ）、ゴム（Ｂ）及び添加剤（Ｃ）を混合することにより樹脂（Ａ）が、連続相で、ゴム（Ｂ）が分散相である熱可塑性エラストマー組成物（Ｄ）を得ることができる。混合方法には特に限定はないが、２軸混練押出機で溶融混合することが好ましい。 According to the present invention, a thermoplastic elastomer composition in which the resin (A) is a continuous phase and the rubber (B) is a dispersed phase by mixing the resin (A), the rubber (B), and the additive (C). A thing (D) can be obtained. The mixing method is not particularly limited, but it is preferable to melt and mix with a twin-screw kneading extruder.
本発明に従えば、樹脂（Ａ）と反応性の官能基（例えば、無水マレイン酸、エポキシ基、カルボキシル基、メチロール基、イソシアネート基、ハロゲン基、アミノ基など）を有する変性ゴム（Ｅ）を第２工程で前記熱可塑性エラストマー組成物（Ｄ）と溶融混合することによって樹脂（Ａ）中の連続相中にゴム（Ｂ）及び変性ゴム（Ｅ）が分散相として分散した所望の熱可塑性エラストマー組成物を得ることができる。変性ゴム（Ｅ）としては、ジエン系ゴム、オレフィン系ゴム等にエポキシ基、カルボキシル基、アミノ基、無水マレイン基等を付与した変性物が挙げられ、この中でも特にイソモノオレフィン−パラアルキルスチレンのハロゲン含有共重合体ゴム、アクリロニトリル−ブタジエン共重合体ゴムのカルボキシル化物が好ましい。また、ゴム（Ｂ）がポリイソブチレン−ポリイソプレン共重合体ゴム又はエチレン−プロピレン−ジエン共重合体ゴムである場合は、変性ゴム（Ｅ）はイソモノオレフィン−パラアルキルスチレンのハロゲン含有享受剛体ゴムであることが好ましく、ゴム（Ｂ）がアクリロニトリル−ブタジエン共重合体ゴムである場合、変性ゴム（Ｅ）はアクリロニトリル−ブタジエン共重合体ゴムのカルボキシル化物であることが好ましい。変性ゴム（Ｅ）の配合量には特に限定はないが好ましくは熱可塑性樹脂（Ａ）１００重量部に対し１０〜４００重量部、更に好ましくは５０〜２５０重量部である。 According to the present invention, the modified rubber (E) having a functional group reactive with the resin (A) (for example, maleic anhydride, epoxy group, carboxyl group, methylol group, isocyanate group, halogen group, amino group, etc.) Desired thermoplastic elastomer in which rubber (B) and modified rubber (E) are dispersed as a dispersed phase in a continuous phase in resin (A) by melt-mixing with said thermoplastic elastomer composition (D) in the second step A composition can be obtained. Examples of the modified rubber (E) include modified products obtained by adding an epoxy group, a carboxyl group, an amino group, an anhydrous maleic group or the like to a diene rubber, an olefin rubber, or the like. A carboxylated product of a halogen-containing copolymer rubber or an acrylonitrile-butadiene copolymer rubber is preferred. When the rubber (B) is a polyisobutylene-polyisoprene copolymer rubber or an ethylene-propylene-diene copolymer rubber, the modified rubber (E) is an isomonoolefin-paraalkylstyrene halogen-containing rigid body rubber. When the rubber (B) is acrylonitrile-butadiene copolymer rubber, the modified rubber (E) is preferably a carboxylated product of acrylonitrile-butadiene copolymer rubber. The blending amount of the modified rubber (E) is not particularly limited, but is preferably 10 to 400 parts by weight, more preferably 50 to 250 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
本発明に係る熱可塑性エラストマー組成物には、前記した必須成分に加えて、可塑剤、架橋剤、加工助剤などの各種添加剤を配合することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the above-described essential components, various additives such as a plasticizer, a crosslinking agent, and a processing aid can be blended with the thermoplastic elastomer composition according to the present invention. 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.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 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.
実施例１〜３及び比較例１〜５
サンプルの調製
表Ｉに示す配合において、ゴムペレタイザーにてペレット化したゴムと樹脂ペレット、添加剤を２軸混練機（ＴＥＸ４４，ＪＳＷ製）に投入し、溶融混練を行った。混練条件は２４０℃×３分で、最大剪断速度１２００ｓ-1であった。材料は押出機から連続してストランド状に押出され、水冷後カッターで切断することによりペレット状の熱可塑性エラストマー組成物を得た。得られた熱可塑性エラストマー組成物と変性ゴムを２軸混練機に投入し、再度溶融混練を行った。混練条件は２４０℃，３minで、最大剪断速度１２００ｓ-1であった。作製した熱可塑性エラストマー組成物のペレットを単軸押出機に投入し、Ｔ−ダイにてシート成形を行った。成形温度は２２０℃、シートは１mm厚に調製した。得られたシートは以下に示す試験法で評価した。結果は表Ｉに示す。
Examples 1-3 and Comparative Examples 1-5
Sample preparation In the formulation shown in Table I, rubber pelletized with a rubber pelletizer, resin pellets, and additives were charged into a twin-screw kneader (TEX44, manufactured by JSW), and melt-kneaded. The kneading conditions were 240 ° C. × 3 minutes and the maximum shear rate was 1200 s −1 . The material was continuously extruded from the extruder into a strand, and was cooled with water and then cut with a cutter to obtain a pellet-shaped thermoplastic elastomer composition. The obtained thermoplastic elastomer composition and modified rubber were put into a twin-screw kneader and melt-kneaded again. The kneading conditions were 240 ° C. and 3 minutes, and the maximum shear rate was 1200 s −1 . The pellets of the produced thermoplastic elastomer composition were put into a single screw extruder, and sheet molding was performed with a T-die. The molding temperature was 220 ° C. and the sheet was 1 mm thick. The obtained sheet was evaluated by the following test method. The results are shown in Table I.
物性評価試験法
１）５０％モジュラス（Ｍ５０)(ＭＰａ）：ＪＩＳ Ｋ−６２５１引張試験法に準じて測定した５０％伸び時の応力
２）テンションセット（％）：ＪＩＳ Ｋ−６２５１引張試験法に準じて、１００％伸張し、戻して３時間放置した後、標線間距離を測定することにより求められた。
Physical property evaluation test method 1) 50% modulus (M50) (MPa): Stress at 50% elongation measured according to JIS K-6251 tensile test method 2) Tension set (%): JIS K-6251 tensile test method Accordingly, it was obtained by measuring the distance between the marked lines after stretching 100%, returning and leaving it for 3 hours.
表Ｉ脚注
＊１（IIR)：イソブチレン・イソプレン共重合ゴム（Exxon MObil Chemical製 Exxon butyl 268）
＊２（EPDM）：エチレン・プリピレン・ジエン共重合ゴム（日本合成ゴム製 JSR EP24）
＊３（NBR)：アクリロニトリル・ブタジエン共重合ゴム（日本ゼオン製 Nipol DN300）
＊４（Br−IPMS）：変性イソモノオレフィン・パラアルキルスチレン（Exxon MObil Chemical製 Exxpro 3035）
＊５（変性NBR)：変性アクリロニトリル・ブタジエン共重合ゴム（日本ゼオン製 Nipol 1072J）
＊６（Ny666)：6-66共重合ナイロン（東レ製 アラミン CM6001FS）
＊７（添加剤１）：アルキルフェノール−ホルムアルデヒド樹脂（田岡化学製 タッキロール 250-1）
＊８（亜鉛華）：酸化亜鉛（大同化学工業製 亜鉛華３号）
＊９（ステアリン酸）：日本油脂製 ビーズステアリン酸
Table I Footnote * 1 (IIR): Isobutylene / isoprene copolymer rubber (Exxon butyl 268 manufactured by Exxon MObil Chemical)
* 2 (EPDM): Ethylene / propylene / diene copolymer rubber (JSR EP24 made by Nippon Synthetic Rubber)
* 3 (NBR): Acrylonitrile-butadiene copolymer rubber (Nipol DN300, manufactured by Nippon Zeon)
* 4 (Br-IPMS): Modified isomonoolefin / paraalkylstyrene (Exxpro 3035 manufactured by Exxon MObil Chemical)
* 5 (Modified NBR): Modified acrylonitrile-butadiene copolymer rubber (Nipol 1072J from Nippon Zeon)
* 6 (Ny666): 6-66 copolymer nylon (Alamin CM6001FS manufactured by Toray)
* 7 (Additive 1): Alkylphenol-formaldehyde resin (Takiroll 250-1 manufactured by Taoka Chemical)
* 8 (Zinc flower): Zinc oxide (Zinc flower No. 3 manufactured by Daido Chemical Industry)
* 9 (Stearic acid): Beads stearic acid made by NOF
熱可塑性エラストマー組成物中のゴムの体積率を増加させる手法として、ステップ混合、相溶化手法などが提案されているが、本発明の特徴は、大小のゴム粒径を意図的に作り出し、ゴム体積率が高く、安定して混合できる熱可塑性エラストマー組成物を提供できることにある。従来の方法で混合した場合、得られるゴム粒径にはばらつきがあり、大小の粒径を制御するのは難しい。ゴム粒径が完全に均一である場合、最大のゴム体積率は約７０％が限度となる。これに対し、本発明によれば、大粒径のゴム分散を得る配合工程（第１工程）と、小粒径のゴム分散を得る配合工程（第２工程）を分け、第１工程→第２工程の順に混合することによって高ゴム体積率の熱可塑性エラストマー組成物を安定して製造することができるので、例えば空気入りタイヤやホース用の材料などとして使用するのに有用である。 As a method for increasing the volume fraction of rubber in the thermoplastic elastomer composition, step mixing, compatibilization method, and the like have been proposed, but the feature of the present invention is to intentionally create a large and small rubber particle size, It is possible to provide a thermoplastic elastomer composition having a high rate and capable of being stably mixed. When mixed by a conventional method, the resulting rubber particle size varies and it is difficult to control the particle size. If the rubber particle size is completely uniform, the maximum rubber volume fraction is limited to about 70%. On the other hand, according to the present invention, the blending step (first step) for obtaining rubber dispersion with a large particle size is separated from the blending step (second step) for obtaining rubber dispersion with a small particle size. Since the thermoplastic elastomer composition having a high rubber volume ratio can be stably produced by mixing in the order of the two steps, it is useful for use as, for example, a material for a pneumatic tire or a hose.
Ａ…熱可塑性樹脂（Ａ）の連続相
Ｂ…ゴム（Ｂ）の分散相
Ｃ…変性ゴム（Ｅ）の分散相
A ... Continuous phase of thermoplastic resin (A) B ... Dispersed phase of rubber (B) C ... Dispersed phase of modified rubber (E)
Claims (5)
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| JP2004020156A JP4428065B2 (en) | 2004-01-28 | 2004-01-28 | Thermoplastic elastomer composition |
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| JP2004020156A JP4428065B2 (en) | 2004-01-28 | 2004-01-28 | Thermoplastic elastomer composition |
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| JP2005213326A true JP2005213326A (en) | 2005-08-11 |
| JP4428065B2 JP4428065B2 (en) | 2010-03-10 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08120131A (en) * | 1994-10-25 | 1996-05-14 | Yokohama Rubber Co Ltd:The | Waterproof sheet |
| JP2000026720A (en) * | 1998-07-10 | 2000-01-25 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and hose |
| JP2000159936A (en) * | 1998-11-25 | 2000-06-13 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and pneumatic tire and hose using the same |
| JP2001019803A (en) * | 1999-07-06 | 2001-01-23 | Sumitomo Rubber Ind Ltd | Thermoplastic elastomer composition and gas hose using the same |
| JP2001049037A (en) * | 1999-08-10 | 2001-02-20 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and hose using the same |
| JP2001261849A (en) * | 2000-03-22 | 2001-09-26 | Yokohama Rubber Co Ltd:The | Method for manufacturing thermoplastic elastomer composition |
-
2004
- 2004-01-28 JP JP2004020156A patent/JP4428065B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08120131A (en) * | 1994-10-25 | 1996-05-14 | Yokohama Rubber Co Ltd:The | Waterproof sheet |
| JP2000026720A (en) * | 1998-07-10 | 2000-01-25 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and hose |
| JP2000159936A (en) * | 1998-11-25 | 2000-06-13 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and pneumatic tire and hose using the same |
| JP2001019803A (en) * | 1999-07-06 | 2001-01-23 | Sumitomo Rubber Ind Ltd | Thermoplastic elastomer composition and gas hose using the same |
| JP2001049037A (en) * | 1999-08-10 | 2001-02-20 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and hose using the same |
| JP2001261849A (en) * | 2000-03-22 | 2001-09-26 | Yokohama Rubber Co Ltd:The | Method for manufacturing thermoplastic elastomer composition |
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| Publication number | Publication date |
|---|---|
| JP4428065B2 (en) | 2010-03-10 |
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