JP6208927B2 - 多層構造体、空気入りタイヤ用インナーライナー及び空気入りタイヤ - Google Patents
多層構造体、空気入りタイヤ用インナーライナー及び空気入りタイヤ Download PDFInfo
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- JP6208927B2 JP6208927B2 JP2012125407A JP2012125407A JP6208927B2 JP 6208927 B2 JP6208927 B2 JP 6208927B2 JP 2012125407 A JP2012125407 A JP 2012125407A JP 2012125407 A JP2012125407 A JP 2012125407A JP 6208927 B2 JP6208927 B2 JP 6208927B2
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- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- KCPNPXFJBCFNRU-UHFFFAOYSA-N pent-4-ene-1,2-diol Chemical compound OCC(O)CC=C KCPNPXFJBCFNRU-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Description
以下に、図を参照しながら、本発明の多層構造体を詳細に説明する。図1は、本発明の多層構造体の一例の断面図である。
本発明の多層構造体1は、図1に示すように、バリア層2と、エラストマー層3とを備える。
そして本発明は、多層構造体1の中で前記エラストマー層3の占める厚さの割合((U1+U2+・・・+Un)/T)が、80%以上であることを特徴とする。
上記の効果に加えて、本発明の多層構造体1は優れた耐疲労性を得ることができる。ゴムのような柔軟性の高い材料からなるエラストマー層3と、柔軟性の低いバリア層2とを張り合わせた状態で、図1に示すように、該多層構造体1の積層方向に対して直角の方向Lに沿って伸長歪みを与えた場合、前記エラストマー層3は弾性変形して元の形状に戻るのに対し、前記バリア層2は耐力点を超えて塑性変形する。ここで、前記エラストマー層3が前記バリア層2に比べて十分に厚い場合、多層構造体全体では弾性変形が優勢となり、塑性変形した前記バリア層2については、圧縮され、前記エラストマー層3上で褶曲する。そして、この褶曲したバリア層2については、従来のバリア層2に比べて方向Lへの引張応力に対して高い耐性を有し、多層構造体全体としての弾性が高くなり、塑性変形を有効に抑制できる結果、極めて高い耐疲労性が得られると考えられる。
また、より優れた耐疲労性を得る点から、前記エラストマー層の占める厚さの割合は、85%以上であることが好ましいく、90%以上であることがより好ましく、95%以上であることがさらに好ましい。
なお、図3(a)〜(d)に示された積層形態の中でも、さらに優れた耐疲労性を得る点からは、厚さの大きなエラストマー層3bで挟んだ図3(b)の多層構造体1がより好ましい。
また、より高い耐クラック性を実現する点から、前記バリア層2の一層あたりの厚さVは、より薄くすることが好ましく、10μm以下であることがさらに好ましい。
本発明による多層構造体を構成するバリア層は、該多層構造体の空気バリア性を実現し、タイヤの内圧を保持するため、ガスバリア性樹脂を含む層である。
G ≦ 1.58−0.0244×E
[式中、Gは1,2−グリコール結合構造単位の含有量(モル%)であり、EはEVOH中のエチレン単位含有量(モル%)であり、但し、E ≦64である]の関係を満たし、且つ、固有粘度が0.05〜0.2L/gの範囲であることが好ましい。このようなEVOHを用いることで、得られるインナーライナーは、ガスバリア性の湿度依存性が小さくなり、良好な透明性及び光沢を有し、他の樹脂からなる層への積層も容易になる。なお、1,2−グリコール結合構造単位の含有量は、「S.Aniyaら,Analytical Science Vol.1,91(1985)」に記載された方法に準じて、EVOH試料をジメチルスルホキシド溶液とし、温度90℃における核磁気共鳴法によって測定されることができる。
本発明の多層構造体を構成するエラストマー層は、多層構造体に耐クラック性や耐クラック性を付与するための層であり、例えば、熱可塑性エラストマーからなる層又は該熱可塑性エラストマーがマトリクスとして存在する熱可塑性エラストマー組成物からなる層などが挙げられる。なお、マトリクスとは、連続相を意味する。上述のバリア層は、ガスバリア性が高く、タイヤの内圧保持性を改良する効果が大きいものの、タイヤ中のゴムに比べ弾性率が大幅に高いため、屈曲時の変形で破断したり、クラックが生じるおそれがある。そのため、エラストマー層を前記バリア層とともに積層するによって、高い多層構造体の内圧保持性及び耐クラック性を確保することができる。
・タイプ1:高分子量ポリ塩化ビニル(PVC)/可塑化ポリ塩化ビニル(PVC)ブレンド型TPVC
ハードセグメントに高分子量のPVCを用いて、ソフトセグメントに可塑剤で可塑化されたPVCを用いてなる熱可塑性エラストマーである。なお、ハードセグメントに高分子量のPVCを用いることで、微結晶部分にて架橋点の働きを持たせている。
・タイプ2:部分架橋PVC/可塑化PVCブレンド型TPVC
ハードセグメントに部分架橋又は分岐構造を導入したPVCを、ソフトセグメントに可塑剤で可塑化されたPVCを用いてなる熱可塑性エラストマーである。
・タイプ3:PVC/エラストマーアロイ型TPVC
ハードセグメントにPVCを、ソフトセグメントに部分架橋ニトリルブタジエンゴム(NBR)等のゴム又はポリウレタン系TPE、ポリエステル系TPE等のTPEを用いてなる熱可塑性エラストマーである。
(1)ポリエステル・ポリエーテル型TPEE
一般には、ハードセグメントとして芳香族系結晶性ポリエステルを、ソフトセグメントとしてポリエーテルを用いた熱可塑性エラストマーである。
(2)ポリエステル・ポリエステル型TPEE
ハードセグメントとして芳香族系結晶性ポリエステルを、ソフトセグメントとして脂肪族系ポリエステルを用いた熱可塑性エラストマーである。
(3)液晶性TPEE
ハードセグメントとして剛直な液晶分子を、ソフトセグメントとして脂肪族系ポリエステルを用いた熱可塑性エラストマーである。
本発明の多層構造体の製造方法としては、上述のバリア層とエラストマー層とが良好に積層・接着可能な方法であれば特に限定されるものではなく、例えば共押出し、はり合わせ、コーティング、ボンディング、付着等の公知の方法が挙げられる。その中でも、本発明の多層構造体の製造方法としては、複数の樹脂組成物を準備し、これら組成物を用いた共押出法によりバリア層を備える多層構造体を製造する方法が好ましい。生産性が高く、層間接着性に優れるためである。
次に、図面を参照しながら、本発明の空気入りタイヤ用インナーライナー及び本発明の空気入りタイヤを詳細に説明する。本発明の空気入りタイヤ用インナーライナーは、上述の多層構造体を用いることを特徴とする。
本発明の空気入りタイヤは、該インナーライナーを備えることを特徴とする。インナーライナー12に上述した多層構造体を適用し、常法により製造することができる。
なお、本発明の空気入りタイヤにおいて、タイヤを構成するゴムと、前記インナーライナー12との張り合わせは、接着剤を用いて行うことができる。
熱可塑性ポリウレタン(TPU)である(株)クラレ製の「クラミロン U9195」を、エラストマー層として用いた。
(株)クラレ製の「エバール F101B」を、エチレン−ビニルアルコール共重合体のバリア層として用いた。
その後、各バリア層の材料と、エラストマー層の材料とを使用し、表1に示す層数及び厚さで積層された多層構造体が形成されるように、バリア層1を用いる場合は、210℃バリア層2を用いる場合は、220℃の溶融物を共押出機からフィードブロックへ供給し、フィードブロックから溶融物を押し出し、多層構造体を作製した。
このようにして得られた多層構造体を、表面温度25℃に保たれ静電印加したキャスティングドラム上で急冷固化した。急冷固化して得られたキャストフィルムを離型紙上に圧着し巻取りを行った。なお、溶融物を合流してからキャスティングドラム上で急冷固化されるまでの時間が約4分となるように流路形状及び総吐出量を設定した。
上記フィルムを、20℃、65%RHで5日間調湿した。得られた調湿済みのフィルムを2枚使用して、モダンコントロール社製MOCON OX−TRAN2/20型を用い、20℃、65%RHの条件下でJIS K7126(等圧法)に準拠して、酸素透過量を測定し、その平均値を求めた。ガスバリア性については、サンプル1の酸素透過量を100としたときの指数によって評価を行い、数値が小さいほど酸素透過量が小さく良好な結果であることを示す。
上記フィルムに、厚さが500μmであるゴム組成物層である補助層を貼付けEBを照射後、接着剤(小笠原ENR接着剤)を塗布し、補助層としての内面に貼り付けて、インナーライナーを作製した。作製したインナーライナーを用いて、図3に示すように、サイズ:195/65R15の乗用車用空気入りタイヤを常法に従って作製した。
作製した空気入りタイヤを、常温(20℃)で、空気圧140kPaで80km/hの速度に相当する回転数のドラム上に荷重6kNで押し付け、20,000kmを走行した。走行後のタイヤショルダー部10cm×10cm当たりのフィルム表面のクラックの数を、耐疲労性の指標として計測した。
上記のように作製したタイヤを、−30℃の雰囲気の中、空気圧140kPaで、80km/hの速度に相当する回転ドラム上に加重6kNで押し付けて10,000km走行させた。そして、走行させたタイヤ(試験タイヤ)を6JJ×15のリムに装着した後、内圧を240kPaとし、3ヶ月間放置した。3ヶ月後の内圧を測定し、下記式:
内圧保持性=((240−b)/(240−a))×100
[式中、aは試験タイヤの3ヶ月後の内圧(kPa)、bは比較例1の試験タイヤの3ヶ月後の内圧(kPa)である]を用いて内圧保持性を評価した。サンプル2の値を100として他の値を指数化した。指数値が大きい程、内圧保持性に優れる。
2 バリア層
3 エラストマー層
7 ビード部
8 サイドウォール部
9 トレッド部
10 カーカス
11 ベルト
12 インナーライナー
13 ビードコア
Claims (7)
- バリア層とエラストマー層とを備える多層構造体において、
前記バリア層及び前記エラストマー層を、交互に、合計で9層以上積層し、
全体の厚さが1〜500μmであり、前記バリア層がエチレン−ビニルアルコール共重合体からなり、該バリア層の一層あたりの厚さが0.001〜10μm以下で、且つ、20℃、65%RHにおける酸素透過量が、10.0 cc・mm/m2・day・atm以下であり、前記エラストマー層の占める厚さの割合が80%以上であることを特徴とする多層構造体。 - 前記バリア層は、20℃、65%RHにおける、ISO 527に準拠した切断時伸びが、100%以下であることを特徴とする請求項1に記載の多層構造体。
- 前記エラストマー層は、20℃、65%RHにおける、ISO 527に準拠した切断時伸びが、100%を超えることを特徴とする請求項1に記載の多層構造体。
- 前記バリア層及び前記エラストマー層が、架橋したフィルムであることを特徴とする請求項1に記載の多層構造体。
- 前記エラストマー層が、ポリスチレン系熱可塑性エラストマー、ポリオレフィン系熱可塑性エラストマー、ポリジエン系熱可塑性エラストマー、ポリ塩化ビニル系熱可塑性エラストマー、塩素化ポリエチレン系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー及びフッ素樹脂系熱可塑性エラストマーの中から選ばれる少なくとも1種を含むことを特徴とする請求項1に記載の多層構造体。
- 請求項1〜5のいずれかに記載の多層構造体を備えることを特徴とする空気入りタイヤ用インナーライナー。
- 請求項6に記載の空気入りタイヤ用インナーライナーを備えることを特徴とする空気入りタイヤ。
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