JP2014012800A - タイヤ用ゴム組成物及び空気入りタイヤ - Google Patents
タイヤ用ゴム組成物及び空気入りタイヤ Download PDFInfo
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- JP2014012800A JP2014012800A JP2012151545A JP2012151545A JP2014012800A JP 2014012800 A JP2014012800 A JP 2014012800A JP 2012151545 A JP2012151545 A JP 2012151545A JP 2012151545 A JP2012151545 A JP 2012151545A JP 2014012800 A JP2014012800 A JP 2014012800A
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- 238000004438 BET method Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【解決手段】ゴム成分100質量部に対して、シリカを1〜150質量部、環化ゴムを0.1〜40質量部、ワックスを0.5〜40質量部、老化防止剤を0.1〜10質量部含むタイヤ用ゴム組成物に関する。
【選択図】なし
Description
前記環化ゴムは、環化天然ゴム、環化イソプレンゴム及び環化ブタジエンゴムからなる群より選択される少なくとも1種であることが好ましい。
サイドウォールに使用されることが好ましい。
なお、シリカの窒素吸着比表面積は、ASTM D3037−81に準じてBET法で測定される値である。
シランカップリング剤としては特に限定されず、従来公知のものを使用でき、例えば、ビス(3−トリエトキシシリルプロピル)テトラスルフィド、ビス(2−トリエトキシシリルエチル)テトラスルフィド、ビス(3−トリメトキシシリルプロピル)テトラスルフィドなどのスルフィド系;3−メルカプトプロピルトリメトキシシランなどのメルカプト系;ビニルトリエトキシシランなどのビニル系;3−アミノプロピルトリエトキシシランなどのアミノ系;γ−グリシドキシプロピルトリエトキシシランなどのグリシドキシ系;3−ニトロプロピルトリメトキシシランなどのニトロ系;3−クロロプロピルトリメトキシシランなどのクロロ系などがあげられる。
なお、カーボンブラックのN2SAは、JIS K 6217−2:2001に準拠して測定される。
なお、Mw/Mnは、GPCによって測定される標準ポリスチレン換算値である。
窒素置換した攪拌機付き耐圧反応器に、脱水トルエン1400g、n−ブチルリチウム18ミリモルを仕込み、内温を60℃に保持した。イソプレン487gを、15分間に亘り連続的に反応器に添加し、内温が75℃を超えないように制御した。その後70℃にて10.5時間反応させ、次いで、重合停止剤として、メタノールを1.4ミリモル添加して、重合反応を停止した。
重合反応を停止した後、80℃に昇温し、p−トルエンスルホン酸4.24gを添加し、80℃に維持した状態で、1時間環化反応を行った。続いて、炭酸ナトリウム1.70gを水5.1gに溶解した水溶液を添加して、環化反応を停止し、反応溶液をろ過して触媒残渣を除去した。この溶液に老化防止剤(イルガノックス1010:チバ・スペシャリティー・ケミカルズ社製)0.4gを添加した後、トルエンを留去し、減圧乾燥して環化ゴム1を得た。
窒素置換した攪拌機付き耐圧容器に、液状ポリイソプレン(クラレ社製 LIR−30:Mn=28,000)300g、トルエン700gを仕込んだ。その混合物を80℃に加温して、ポリイソプレンを完全に溶解した後、p−トルエンスルホン酸2gを添加し、内温を80℃に維持しながら環化反応を行った。1時間反応後、炭酸ナトリウム0.8gを含む炭酸ナトリウム25%水溶液を添加して反応を停止し、80℃で30分間攪拌後、ろ過して触媒残渣を除去した。この溶液に老化防止剤(イルガノックス1010:チバ・スペシャリティー・ケミカルズ社製)0.3gを添加した後、トルエンを留去し、減圧乾燥して環化ゴム2を得た。
液状ポリイソプレンに代えて、液状ポリブタジエン(サートマー社製、ライコン150、Mn=5,200)を用いた以外は、製造例2と同様にして、環化ゴム3を得た。
液状ポリイソプレンに代えて、ポリブタジエン(宇部興産社製、UBEPOL 150L、Mn=250,000)を用い、環化反応時間を3時間に変更した以外は製造例2と同様にして環化ゴム4を得た。
環化ゴムの環化率は、BRUKER社製AV400のNMR装置、データー解析ソフトTOP SPIN2.1を用いて1H−NMR測定により、環化反応前後におけるポリマー中のプロトンのピーク面積比により求めた。なお、詳しい環化率計算方法は、下記の文献に記載のとおりである。
Y.Tanaka and H.Sato,J.Polym.Sci: Poly.Chem.Ed.,17,3027(1979)
ポリスチレンを標準物質、テトラヒドロフランを溶媒とし、温度40℃において、環化ゴムのゲルパーミエーション(透過)クロマトグラフィー(GPC、東ソー株式会社製)を行い、得られた分子量分布曲線から求めた検量線を用いて計算し、Mn、Mwを求めた。
環化ゴムのガラス転移温度を、示差走査熱量計(セイコー電子工業(株)製:SSC5200)を用いて、開始温度−100℃、昇温速度10℃/分の条件で測定した。
2mm角に裁断した試料0.2gを、トルエン100mlに、48時間浸漬した後、80メッシュの金網上に残るゲル分の乾燥重量の割合を百分率で示した。
NR:RSS#3
BR:宇部興産(株)製のUBEPOL BR150B(シス1,4結合量97%、ML1+4(100℃)40、Mw/Mn3.3)
環化ゴム1〜4:製造例1〜4
シリカ:EVONIK−DEGUSSA社製のウルトラジルVN3(N2SA:175m2/g)
カーボンブラック:新日化カーボン(株)製のニテロン#55S(N2SA:28×103m2/kg)
シランカップリング剤:EVONIK−DEGUSSA社製のSi69(ビス(3−トリエトキシシリルプロピル)テトラスルフィド)
ワックス1:日本精蝋(株)製のオゾエース0355
ワックス2:東亜化成(株)製のTOA−200229(天然系混合ワックス、配合:カルナバワックス30質量%、キャンデリラワックス30質量%、ライスワックス20質量%、ミツロウ20質量%)
ステアリン酸:日油(株)製のステアリン酸「桐」
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛2種
老化防止剤:大内新興化学工業(株)製のノクラック6C(N−(1,3−ジメチルブチル)−N−フェニル−p−フェニレンジアミン)
硫黄:鶴見化学工業(株)製の粉末硫黄
加硫促進剤:大内新興化学工業(株)製のノクセラーNS(N−tert−ブチル−2−ベンゾチアゾリルスルフェンアミド)
表2の配合処方にしたがい、(株)神戸製鋼所製の1.7Lバンバリーミキサーを用いて、硫黄および加硫促進剤以外の薬品を充填率が58%になるように充填し、80rpmで140℃に到達するまで混練りして混練り物を得た。次に、オープンロールを用いて、得られた混練り物に硫黄および加硫促進剤を添加して混練りし、未加硫ゴム組成物を得た。
さらに、得られた未加硫ゴム組成物を所定のサイズに成形し、150℃の条件下で20分間プレス加硫することにより加硫ゴム組成物を得、約2mm×130mm×130mmの加硫ゴムスラブシートを作製した。
(株)岩本製作所製の粘弾性スペクトロメーターVESを用いて、温度70℃、初期歪10%、動歪2%および周波数10Hzの条件下で加硫ゴムスラブシートの損失正接(tanδ)を測定し、比較例1の転がり抵抗指数を100とし、下記計算式により、転がり抵抗を指数表示した。転がり抵抗指数が大きいほど、転がり抵抗が低減され、好ましいことを示す。
(転がり抵抗指数)=(比較例1のtanδ)/(各配合のtanδ)×100
加硫ゴムスラブシートについて、JIS K 6259「加硫ゴム及び熱可塑性ゴム−耐オゾン性の求め方」に基づき、オゾン濃度50±5pphm、50℃、伸張歪20±2%の条件下で、48時間試験した後の亀裂の状態を観察することで、耐オゾン性を評価した。なお、評価方法は、JISに記載の方式に従い、亀裂の数と大きさを表した。アルファベット(A、B及びC)は、Aが亀裂の数が少なく、Cが亀裂の数が多いことを示し、数字(1〜5)は、大きいほど、亀裂の大きさが大きいことを示し、「クラックなし」は、クラックが発生しなかったことを示す。また「破断」は、クラックでとどまらず、試験片が大きく損傷していることを示す。
試験用タイヤにホィールを取り付け、2.2気圧の空気を封入して、屋外(神戸市内)に3ヶ月間放置し、その後の変色度合いを目視で評価した。
白色化:○:変色なし △:わずかに白色化 ×:激しく白色化
茶変色:○:変色なし △:わずかに茶変色 ×:激しく茶変色
Claims (6)
- ゴム成分100質量部に対して、シリカを1〜150質量部、環化ゴムを0.1〜40質量部、ワックスを0.5〜40質量部、老化防止剤を0.1〜10質量部を含むタイヤ用ゴム組成物。
- 前記環化ゴムの環化率が0.1〜40%である請求項1記載のタイヤ用ゴム組成物。
- 前記環化ゴムは、環化天然ゴム、環化イソプレンゴム及び環化ブタジエンゴムからなる群より選択される少なくとも1種である請求項1又は2記載のタイヤ用ゴム組成物。
- 前記ゴム成分100質量部に対して、カーボンブラックを1〜50質量部含む請求項1〜3のいずれかに記載のタイヤ用ゴム組成物。
- サイドウォールに使用される請求項1〜4のいずれかに記載のタイヤ用ゴム組成物。
- 請求項1〜5のいずれかに記載のゴム組成物を用いて作製したサイドウォールを有する空気入りタイヤ。
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JP2017052851A (ja) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | ゴム組成物およびそれを用いたタイヤ |
Citations (4)
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JPH04148922A (ja) * | 1990-10-12 | 1992-05-21 | Toyo Tire & Rubber Co Ltd | コード化した製品情報を内面に表示した空気入りタイヤの製造法 |
JP2004059890A (ja) * | 2002-07-31 | 2004-02-26 | Yamashita Rubber Co Ltd | 接着性ゴム組成物 |
JP2007308624A (ja) * | 2006-05-19 | 2007-11-29 | Sumitomo Rubber Ind Ltd | サイドウォール用ゴム組成物 |
JP2008303329A (ja) * | 2007-06-08 | 2008-12-18 | Sumitomo Rubber Ind Ltd | サイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04148922A (ja) * | 1990-10-12 | 1992-05-21 | Toyo Tire & Rubber Co Ltd | コード化した製品情報を内面に表示した空気入りタイヤの製造法 |
JP2004059890A (ja) * | 2002-07-31 | 2004-02-26 | Yamashita Rubber Co Ltd | 接着性ゴム組成物 |
JP2007308624A (ja) * | 2006-05-19 | 2007-11-29 | Sumitomo Rubber Ind Ltd | サイドウォール用ゴム組成物 |
JP2008303329A (ja) * | 2007-06-08 | 2008-12-18 | Sumitomo Rubber Ind Ltd | サイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ |
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JP2017052851A (ja) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | ゴム組成物およびそれを用いたタイヤ |
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