JP6151991B2 - 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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- JP6151991B2 JP6151991B2 JP2013141961A JP2013141961A JP6151991B2 JP 6151991 B2 JP6151991 B2 JP 6151991B2 JP 2013141961 A JP2013141961 A JP 2013141961A JP 2013141961 A JP2013141961 A JP 2013141961A JP 6151991 B2 JP6151991 B2 JP 6151991B2
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- 239000003784 tall oil Substances 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Landscapes
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Description
また、上記特定の界面活性剤は、ワックスや老化防止剤とともにタイヤ表面にブルームし、それらを溶かし平坦化するため、白変色を軽減できると共に、タイヤ表面に形成される表面保護層の凹凸が減り、乱反射により目立つ茶変色を大幅に軽減できる。また、黒光りの光沢をタイヤ表面に与えることもできる。また、耐オゾン性も改善できる。
更に、上記天然由来ワックスと、上記特定の界面活性剤とを併用することにより、良好な破断時伸びを維持又は改善しながら、耐変色性、耐オゾン性を相乗的に改善でき、広い温度域で優れた耐オゾン性が得られるとともに、変色も充分に抑制できる。
プルロニック型非イオン界面活性剤は、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリプロピレングリコールエチレンオキシド付加物とも呼ばれ、一般的には、下記式(I)で表わされる非イオン界面活性剤である。下記式(I)で表わされるように、プルロニック型非イオン界面活性剤は、両側にエチレンオキシド構造から構成される親水基を有し、この親水基に挟まれるように、プロピレンオキシド構造から構成される疎水基を有する。
NR:TSR20
IR:IR2200
BR1:日本ゼオン(株)製のBR1250H(リチウム開始剤を用いて重合したスズ変性BR、ビニル含量:10〜13質量%、Mw/Mn:1.5、スズ原子の含有量:250ppm)
BR2:宇部興産(株)製のVCR617(SPB含有BR、SPBの含有量:17質量%、SPBの融点:200℃)
BR3:ランクセス社製のBUNA−CB25
SBR:日本ゼオン(株)製のSBR1502
EPDM:住友化学(株)製のEsprene502
カーボンブラック(N550):キャボットジャパン(株)製のショウブラックN550(N2SA:42m2/g、DBP吸油量:115ml/100g)
オイル:H&R社製のvivatec500(TDAE、Low Polycyclic Aroma Oil)
ステアリン酸:日油(株)製のステアリン酸「椿」
酸化亜鉛:東邦亜鉛(株)製の銀嶺R
硫黄:日本乾溜工業(株)製のセイミ硫黄OT(不溶性硫黄、オイル10%含有)
加硫促進剤TBBS: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)
架橋助剤:田岡化学工業(株)製のタッキロールV200(アルキルフェノール・塩化硫黄縮合物)
石油由来ワックス1:試作品(ノルマルアルカン分:平均85質量%)
石油由来ワックス2:日本精鑞(株)製のパラフィンワックス−125(PW−125)(ノルマルアルカン分:平均88質量%)
天然由来ワックス1:横関油脂工業(株)製の精製ライスワックスS−100(軟化点分布:77〜83℃、エステル成分:95質量%、遊離脂肪酸:4質量%、遊離アルコール:1質量%、炭化水素:1質量%)
天然由来ワックス2:東亜化成(株)製のライスワックスTOWAX 37F(軟化点分布:75〜81℃、エステル成分:90質量%以上、遊離脂肪酸:5質量%、遊離アルコール:2質量%、炭化水素:1質量%)
天然由来ワックス3:横関油脂工業(株)製の精製ミツロウBEESWAXCO−100(軟化点分布:0〜75℃、エステル成分:70質量%、遊離脂肪酸:14質量%、遊離アルコール:2質量%、炭化水素:14質量%)
天然由来ワックス4:下記製造例で調製した精製砂糖きびワックス(軟化点分布:73〜79℃、エステル成分:61.4質量%、遊離脂肪酸:13質量%、遊離アルコール:4質量%、炭化水素:22質量%)
<界面活性剤1>:三洋化成工業(株)製のイオネットDO600(主成分が、式(2)のR2及びR3:−C17H33、式(2)のe:12、下式で表わされる化合物)
<界面活性剤4>:三洋化成工業(株)製のニューポールPE−74(プルロニック型非イオン界面活性剤(PEG/PPG−30/35コポリマー)(上記式(I)のa+c:30、b:35)
<界面活性剤5>:関東化学(株)製のモノステアリン酸ポリオキシエチレンソルビタン
<界面活性剤6>:関東化学(株)製のトリオレイン酸ポリオキシエチレンソルビタン
<界面活性剤7>:関東化学(株)製のポリオキシエチレンドデシルエーテル
<界面活性剤8>:東京化成工業(株)製のエチレングリコールジブチルエーテル
老化防止剤6C:住友化学(株)製のアンチゲン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(6PPD))
老化防止剤6QDI:フレキシス社製の6QDI(N−(1,3−ジメチルブチル)−N’−フェニルキノンジイミン)
老化防止剤TMQ:大内新興化学工業(株)製ノクラック224(2,2,4−トリメチル−1,2−ジヒドロキノリン重合体)
粗糖製造工程で砂糖きびを圧搾して絞り取った砂糖ジュースを静置し、ジュース上部に浮上してくる主として繊維分と油脂分からなる浮遊物を濾過分離して得られるフィルターケーキを真空恒温槽で乾燥し、乾燥ケーキを得た。この乾燥ケーキを、撹拌機と還流冷却器、そして加熱ヒーターを備えた容器に入れ、抽出溶媒を加え、撹拌しながら加熱して溶媒の還流温度で抽出した。抽出が終了した後直ちに濾過を行い、フィルターケーキを分離除去した。濾過液を静置して下層の水層を分離した後、溶媒層を蒸留し、溶媒を除去して深緑色の砂糖きび粗ワックスを得た。得られた砂糖きびワックスを常法に従って溶剤精製し、溶媒を蒸留で除去した後、更にこれを常法に従い漂白、脱臭処理して精製砂糖きびワックスを得た。
測定装置としてキャピラリーGC、カラムとしてアルミニウムコーティングされたキャピラリーカラムを用い、キャリアガスヘリウム、流量4ml/分、カラム温度180〜390℃、昇温速度15℃/分の条件にて測定した。
表1〜2に示す配合処方にしたがい、(株)神戸製鋼製1.7Lバンバリーミキサーを用いて、硫黄、架橋助剤及び加硫促進剤以外の薬品を混練りした。次に、オープンロールを用いて、得られた混練り物に硫黄、架橋助剤及び加硫促進剤を添加して練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を用いて、トレッド、ウイング、サイドウォール、クリンチの形状に合わせて成形し、他のタイヤ部材とともに貼り合わせて未加硫タイヤを作製し、170℃で加硫して試験用タイヤ(205/65R15)を得た。得られた試験用タイヤの性能を以下の試験により評価した。
タイヤのサイドウォールから試験ゴムを切り出した。次に、JIS K6253に準拠し、25℃の温度で硬度計を用いて、切り出した試験ゴムの硬度を測定(ショア−A測定)した。硬度は、54±1になる様に、配合調整し、破断時伸び(EB)を比較可能とした。
タイヤのサイドウォールから試験ゴムを切り出した。次に、切り出した試験ゴムから3号ダンベル型を用いて試験片を作成し、JIS K 6251「加硫ゴム及び熱可塑性ゴム−引張特性の求め方」に準じて、室温にて引張試験を実施し、破断時伸びEB(%)を測定し、比較例1のEBを100とした指数(各配合のEB/比較例1のEB×100)を計算した。指数が大きいほど、破断時伸びに優れることを示す。なお、EB指数は95以上を目標とした。
高温地域は中近東アラブ首長国連邦で約1年間(夏を含む)、亜寒冷地域は北海道で約1年間(冬を含む)ロードテストを行い、発生したクラックの度合いを、以下の基準にしたがって評価した。数字が大きいほど、耐オゾン性(耐クラック性能)に優れていることを示す。なお、3+以上を目標とした。
1:3mm以上の亀裂または切断が見られる。
2:1mm以上3mm未満の深い亀裂が見られる。
3:1mm未満の深くて比較的大きな亀裂が見られる。
4:肉眼では、やっとのことで亀裂または切断が確認できる。
5:肉眼では確認できないが、拡大鏡(10倍)では亀裂または切断が確認できる。
(1)屋外:茶変色評価
神戸にて、タイヤを屋外の日の当たる場所に6カ月間(冬〜夏)放置し、色差度計を用いて、a*、b*を測定し、その値により、以下の基準にしたがって5段階に分けて評価した。数字が大きいほど、茶変色の度合いが小さいことを示す。なお、3+以上を目標とした。
(基準)
1:−(a*+b*)×10≦−30
2:−30<−(a*+b*)×10≦−20
3:−20<−(a*+b*)×10≦−10
4:−10<−(a*+b*)×10≦0
5:−(a*+b*)×10>0
神戸にて、タイヤを屋内の倉庫に6カ月間(冬〜夏)放置し、色差度計を用いて、L*を測定し、その値により、以下の基準にしたがって5段階に分けて評価した。数字が大きいほど、白変色の度合いが小さいことを示す。なお、3+以上を目標とした。
(基準)
1:100−L*≦60
2:60<100−L*≦65
3:65<100−L*≦70
4:70<100−L*≦75
5:100−L*>75
Claims (5)
- ゴム成分と、エステル成分含有量が40〜98質量%の天然由来ワックスと、フェニレンジアミン系及び/又はキノン系老化防止剤と、非イオン界面活性剤とを含み、
前記非イオン界面活性剤が、下記式(1)及び/又は下記式(2)で表される非イオン界面活性剤、並びに、プロピレンオキシド構造から構成される疎水基の両側に、エチレンオキシド構造から構成される親水基を有し、下記式(I)で表される非イオン界面活性剤からなる群より選択される少なくとも1種であり、
ゴム成分100質量%中のジエン系ゴムの含有量が70〜100質量%であり、
ゴム成分100質量部に対して、前記天然由来ワックスの含有量が0.01〜5.0質量部、石油由来ワックスの含有量が0〜6.0質量部、前記フェニレンジアミン系及び前記キノン系老化防止剤の合計含有量が1.0〜8.0質量部、前記非イオン界面活性剤の含有量が0.1〜5.0質量部であるタイヤ用ゴム組成物。
- 前記天然由来ワックスは、イネ科植物から抽出され、軟化点60〜90℃の成分からなるものである請求項1記載のタイヤ用ゴム組成物。
- 前記石油由来ワックス100質量%中の炭素数20〜32の各ノルマルアルカンの合計含有率が25〜50質量%、炭素数33〜44の各ノルマルアルカンの合計含有率が25〜50質量%である請求項1又は2記載のタイヤ用ゴム組成物。
- タイヤ外層用ゴム組成物である請求項1〜3のいずれかに記載のタイヤ用ゴム組成物。
- 請求項1〜4のいずれかに記載のゴム組成物を用いて作製した空気入りタイヤ。
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FR3059596A1 (fr) | 2016-12-02 | 2018-06-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pourvu d'un flanc externe comportant un elastomere thermoplastique comprenant au moins un bloc elastomere sature |
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CN110352216B (zh) * | 2017-03-15 | 2022-05-03 | 住友橡胶工业株式会社 | 胎侧壁用橡胶混合物以及充气轮胎 |
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