JP6827939B2 - ゴム補強用繊維、ゴム−繊維複合体およびこれを用いた空気入りタイヤ - Google Patents
ゴム補強用繊維、ゴム−繊維複合体およびこれを用いた空気入りタイヤ Download PDFInfo
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- JP6827939B2 JP6827939B2 JP2017545506A JP2017545506A JP6827939B2 JP 6827939 B2 JP6827939 B2 JP 6827939B2 JP 2017545506 A JP2017545506 A JP 2017545506A JP 2017545506 A JP2017545506 A JP 2017545506A JP 6827939 B2 JP6827939 B2 JP 6827939B2
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- rubber
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- olefin
- fiber
- resin
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 10
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- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 1
- HSMJHYIKSKAADV-UHFFFAOYSA-M sodium;n,n-didecylcarbamodithioate Chemical compound [Na+].CCCCCCCCCCN(C([S-])=S)CCCCCCCCCC HSMJHYIKSKAADV-UHFFFAOYSA-M 0.000 description 1
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- NMACXHISEGVEII-UHFFFAOYSA-M sodium;octoxymethanedithioate Chemical compound [Na+].CCCCCCCCOC([S-])=S NMACXHISEGVEII-UHFFFAOYSA-M 0.000 description 1
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- PGGWALFSVWIQLA-UHFFFAOYSA-M sodium;propoxymethanedithioate Chemical compound [Na+].CCCOC([S-])=S PGGWALFSVWIQLA-UHFFFAOYSA-M 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical class C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
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- WKPMJWCYKAGOLT-UHFFFAOYSA-L zinc;n,n-didodecylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCCCCCN(C([S-])=S)CCCCCCCCCCCC.CCCCCCCCCCCCN(C([S-])=S)CCCCCCCCCCCC WKPMJWCYKAGOLT-UHFFFAOYSA-L 0.000 description 1
- YTKAYKIKGOITDD-UHFFFAOYSA-L zinc;n,n-diheptylcarbamodithioate Chemical compound [Zn+2].CCCCCCCN(C([S-])=S)CCCCCCC.CCCCCCCN(C([S-])=S)CCCCCCC YTKAYKIKGOITDD-UHFFFAOYSA-L 0.000 description 1
- VSWBCXJHSLMWFY-UHFFFAOYSA-L zinc;n,n-dihexylcarbamodithioate Chemical compound [Zn+2].CCCCCCN(C([S-])=S)CCCCCC.CCCCCCN(C([S-])=S)CCCCCC VSWBCXJHSLMWFY-UHFFFAOYSA-L 0.000 description 1
- JGSUMMPGKPITGK-UHFFFAOYSA-L zinc;n,n-dipentylcarbamodithioate Chemical compound [Zn+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC JGSUMMPGKPITGK-UHFFFAOYSA-L 0.000 description 1
- QUPAJUAGQJQKQE-UHFFFAOYSA-L zinc;n,n-dipropylcarbamodithioate Chemical compound [Zn+2].CCCN(C([S-])=S)CCC.CCCN(C([S-])=S)CCC QUPAJUAGQJQKQE-UHFFFAOYSA-L 0.000 description 1
- XCZHWCHDGLXWQU-UHFFFAOYSA-L zinc;octoxymethanedithioate Chemical compound [Zn+2].CCCCCCCCOC([S-])=S.CCCCCCCCOC([S-])=S XCZHWCHDGLXWQU-UHFFFAOYSA-L 0.000 description 1
- WKEANFGAGCEWSA-UHFFFAOYSA-L zinc;pentoxymethanedithioate Chemical compound [Zn+2].CCCCCOC([S-])=S.CCCCCOC([S-])=S WKEANFGAGCEWSA-UHFFFAOYSA-L 0.000 description 1
- SZNCKQHFYDCMLZ-UHFFFAOYSA-L zinc;propan-2-yloxymethanedithioate Chemical compound [Zn+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S SZNCKQHFYDCMLZ-UHFFFAOYSA-L 0.000 description 1
- GPTVLJQJAOTUCP-UHFFFAOYSA-L zinc;propoxymethanedithioate Chemical compound [Zn+2].CCCOC([S-])=S.CCCOC([S-])=S GPTVLJQJAOTUCP-UHFFFAOYSA-L 0.000 description 1
- LVLIEOIPDYPFNY-UHFFFAOYSA-L zinc;tetracosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O LVLIEOIPDYPFNY-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C9/12—Carcasses built-up with rubberised layers of discrete fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/48—Bead-rings or bead-cores; Treatment thereof prior to building the tyre
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C9/023—Carcasses built up from narrow strips, individual cords or filaments, e.g. using filament winding
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C2009/0269—Physical properties or dimensions of the carcass coating rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C15/0628—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer
- B60C2015/0692—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer characterised by particular materials of the cords
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Multicomponent Fibers (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
前記樹脂材料(B)が、オレフィン系重合体(X)と、加硫促進剤(F)と、を含有することを特徴とするものである。
本発明のゴム補強用繊維は、芯部が融点150℃以上の高融点樹脂(A)からなり、鞘部が、高融点樹脂(A)よりも融点の低い樹脂材料(B)からなる芯鞘型の複合繊維よりなるものである。
なお、加硫促進剤(F)とは、硫黄を用いるゴムの加硫で、ゴムと硫黄との反応が非常に遅いため、「硫黄のS8環の開環を促進するための活性化チールラジカルを発生させるもの、または塩基性物質で硫黄と反応してポリスルフィドを経由して硫黄を活性化させるもの」「加硫促進剤としては、硫黄を活性化しうるチールラジカルを発生するようなチアゾール系、スルフェンアミド系、チラリウム系、ジチオカルバミン酸系と、塩基性のアルデヒド・アミン縮合物およびグアニジン系など」(渡邊隆、平田靖著:“ゴム用添加剤活用技術”;株式会社工業調査会発行、頁31および頁32)で、通常は、加硫を促進する目的でゴム組成物に配合する化合物である。従って本発明のように、ゴムと複合化する繊維などの樹脂組成物に混合して、加硫時の樹脂側の改質で配合を検討された例は、これまでに特にみられない。
また、このような電荷移動相互作用が働くと、ゴム中にあった硫黄成分が鞘部の樹脂材料の表面や内部に移行することが促進される。本発明者の走査型電子顕微鏡を用いたエネルギー分散型X線分光法による硫黄原子分布の元素分析(EDX)での検討では、加硫促進剤(F)を含めると、鞘部の樹脂材料の界面に分布する硫黄成分量が多くなる傾向があり、場合によっては、本来は硫黄成分がない鞘部の樹脂材料の界面より内側に、被着ゴム中から移行する硫黄成分が分布するようになることが分かった。このように、加硫促進剤(F)により、ゴムとの界面の相互作用が増大することにより、ひいては接着性をより向上することができる。
また、この多加硫物が繊維に含有されるジエン部分と被着ゴム間で共加硫すると、ゴムとの接着性を更に向上させることができる。
なお、ゴム補強用芯鞘繊維の鞘部の樹脂材料(B)は、硫黄により架橋が可能なジエンを含む成分を含んでいるが、加硫促進剤成分を含有していないときは、被着ゴム中からの電荷移動相互作用による硫黄成分の移行は少なくなる。また更に、硫黄成分が移行しても加硫促進剤により多加硫物の中間体が得られないので、工業的なゴム加硫工程の時間では、加硫促進剤が配合されてないゴム組成物の加硫が非常に遅くて加硫できないことと同様の理由で、ゴム補強用芯鞘繊維の鞘部の樹脂材料(B)においても、同様にジエン部位の加硫が非常に遅くなり硫黄分による架橋が殆ど得られないため、接着向上の効果を得ることができない。
エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミン、ポリエチレンイミン等に挙げられる非環式ポリアミン及びその誘導体並びにその塩、
シクロヘキシルアミンなどの脂環式ポリアミン及びその誘導体並びにこれらの塩、
ヘキサメチレンテトラミンなどの脂環式ポリアミン及びその誘導体並びにこれらの塩、アニリン、アルキルアニリン、ジフェニルアニリン、1−ナフチルアニリン、N−フェニル−1−ナフチルアミン等に挙げられる芳香族モノアミン及びその誘導体ならびにこれらの塩、
フェニレンジアミン、ジアミノトルエン、N‐アルキルフェニレンジアミン、ベンジジン、グアニジン類、n−ブチルアルデヒドアニリン、などの芳香族ポリアミン化合物及びその誘導体、などが挙げられる。
なお、グアニジン類としては、1,3−ジフェニルグアニジン、1,3−ジ−o−トリルグアニジン、1−o−トリルビグアニド、ジカテコールボレートのジ−o−トリルグアニジン塩、1,3−ジ−o−クメニルグアニジン、1,3−ジ−o−ビフェニルグアニジン、1,3−ジ−o−クメニル−2−プロピオニルグアニジン等が挙げられる。これらのうち1,3−ジフェニルグアニジンが反応性が高いので好ましい。
また、例えば、窒素原子以外のヘテロ原子を有する複素環式化合物としては、オキサゾリン、チアゾリン等の窒素およびその他のヘテロ原子を含有する複素環式化合物及びその誘導体が挙げられる。
この理由は、ルイス塩基性化合物(F1)の極性が強いと、鞘部の樹脂材料(B)に含まれるオレフィン重合体(X)が無極性のポリマーのときには、樹脂材料(B)に溶けにくくなり、樹脂表面にブルームした層を形成しやすくなるためであり、ルイス塩基性化合物(F1)はルイス塩基部分に有する活性水素が少なく極性が低い方が、樹脂材料(B)と被着ゴムとの間での析出物による不具合が発生しにくくなるため、好ましい。
前記ルイス塩基部位に活性水素を1つ有するルイス塩基化合物(F12)としては、ルイス塩基部分に活性水素を1つ有するルイス塩基性化合物であれば特に制限されないが、例えば、窒素含有化合物であれば、非環式第2級アミン化合物、脂環式第2級ポリアミン化合物、芳香族第2級アミン化合物など、不対電子を供与することができる窒素原子に活性水素を1つ有する化合物が挙げられる。
具体的には、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、水酸化銅などの金属水酸化物;酸化マグネシウム、酸化カルシウム、酸化亜鉛(亜鉛華)、酸化銅などの金属酸化物;炭酸マグネシウム、炭酸カルシウム、炭酸ナトリウム、炭酸リチウム、炭酸カリウムなどの金属炭酸化物が挙げられる。
これらの中でも、アルカリ金属塩としては、金属水酸化物が好ましく、特に水酸化マグネシウムが好適である。
なお、これら金属塩は、加硫助剤に分類されることもあるが、本発明においては、加硫促進剤に分類する。
これらのうち、N−エチル−N−フェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオカルバミン酸亜鉛は、反応性が高いため望ましい。また、促進剤化合物に含まれるアルキル基が大きくなると比較的に無極性であるポリマーの場合では溶解度が高くなる傾向があり、析出などによる表面性状の悪化による紡糸性の低下などが発生しにくいため、ジブチルジチオカルバミン酸亜鉛などは、特に好ましい例である。
なお、これらの硫黄の移行については、鞘部の樹脂材料とゴムとの界面について走査型電子顕微鏡を用いた電子線照射によるエネルギー分散型X線分光法で元素分析(EDX)を行い、被着ゴム中の硫黄分ピークのカウントの平均レベルに対する、鞘部の樹脂材料とゴムとの界面や、鞘部の樹脂材料内に分布する硫黄分のカウントの大きさにより、ゴム中の硫黄が鞘部の樹脂材料に移行する傾向を解析することが可能である。
加硫促進剤(F)の量が0.2質量部以上になると、被着ゴム側の硫黄成分の分布より鞘部の樹脂材料界面から樹脂材料の内部側で分布する硫黄成分量が多くなり、0.7質量部以上で、加硫促進剤(F)や樹脂材料(B)の組み合わせなどで、場合によっては、被着ゴム中に含まれる硫黄のEDXのカウント数による分布量よりも、鞘部の樹脂材料側に移行した硫黄の分布が多くなる場合もあり、ゴム接着性がより向上されるため好ましい。
一方、加硫促進剤(F)の量が20質量部を超過すると、樹脂材料(B)内で加硫促進剤(F)が均一に分布せず相分離することがあり、鞘部の樹脂材料の凝集破壊抗力が低下し、樹脂材料内が剥離しやすくなって、ゴムとの接着性が低下する場合がある。
また、加硫促進剤(F)の量が5質量部超過であると、極性が高い加硫促進剤が極性の低い鞘部の樹脂材料に溶けにくいときに、紡糸後に樹脂表面にブルームすると、融着不良や外観不良を起こす場合がある。
この理由は、ルイス塩基性官能基を含む付加重合可能なモノマーを5モル%より多く含むと、本発明の加硫促進剤(F)を含有しなくても、鞘部を構成する樹脂材料(B)のオレフィン系重合体の塩基性官能基を含有することで、電子対供与によって加硫を促進する効果が得られるため、本発明の接着向上の効果が少なくなるためである。
また、極性があるルイス塩基性官能基を含む付加重合可能なモノマーの含量が多くなると、被着ゴム組成物に含まれる、ブタジエンゴム、スチレンブタジエンゴム、イソプレンゴム、天然ゴムなどの極性の小さいゴムポリマーに対して、鞘部を構成する樹脂材料(B)のオレフィン重合体のポリマーの極性が大きくなるため、熱下のポリマー同士の相溶性が低下して、鞘部の樹脂材料(B)と被着ゴムとの融着が起こりにくくなるためである。
これらのうち、繰り返し単位となるモノマー1000個に対し40個以下程度の他のモノマーを含むものを、オレフィン系共重合体(D)として用いることができる。
この場合の、ジエン成分を含むオレフィン系ランダム共重合体(C2)におけるジエン含有量は、好適には、1〜20質量%、より好ましくは3〜15質量%である。さらに、本発明において、オレフィン系ホモ重合体若しくはオレフィン系共重合体(D)((C)を除く)としては、ポリプロピレンやポリエチレンを好適に用いることができる。
この理由は、本発明の芯鞘構造繊維の鞘部の樹脂材料(B)においては、繊維の溶融紡糸における糸状紡糸で、芯部の樹脂材料が紡糸応力を主に負担するため、鞘部の樹脂マトリックスとなるポリマーが、EPDMなどの共役ジエンを含むオレフィン系共重合体(C2)で、無定形かつ軟質の高分子物質であるゴム状重合体でも、糸状を生成した芯部の樹脂に鞘成分が表面に被覆するため、紡糸することが可能であるためである。
しかしながら、ゴム状重合体であると、例えば紡糸速度が速いときには、紡糸加工時に表面の荒れ等の不具合が生じやすい。このため、例えば、従来より用いられるプロピレンとエチレンとの共重合体などのオレフィン系ランダム共重合体(C)を主成分として、ジエンを含むゴム状の共重合体よりは剛性が高い成分を副成分として混合すると、紡糸での加工性が容易となるので好ましい。
例えば、ジエン成分を含むオレフィン系ランダム共重合体(C2)としては、EPDMの他に、スチレンとブタジエンとの共重合体、イソブテンとイソプレンとの共重合体などが挙げられ、オレフィン系ホモ重合体若しくはオレフィン系共重合体(D)((C)を除く)としては、ポリブタジエン、ポリイソプレン、ポリノルボルネンなどが挙げられる。
なお、本発明におけるブロック共重合体は、2種類以上のモノマー単位からなる高分子であって、その少なくとも1つのモノマー単位が、主として長く連続して配列してなる単独分子鎖(ブロック)を形成している共重合体を意味する。また、スチレン系ブロック共重合体は、スチレン単量体を主として長く連結して配列したブロックを含むブロック共重合体を意味する。
また、他のスチレン系エラストマーとしては、ポリオレフィン樹脂を主鎖、ビニル系ポリマーを側鎖に持つオレフィン系グラフト共重合体などのスチレン系エラストマーが挙げられる。グラフト共重合体は、幹となる共重合にところどころに枝のように他の重合体が配列した重合体であるが、本発明においては、スチレン単量体を主として長く連結して配列したブロックを含むグラフト共重合体をスチレン系グラフトポリマーとする。
スチレン系グラフトポリマーとしては、低密度ポリエチレンを主鎖としてポリスチレンを側鎖に持つオレフィン系グラフト共重合体(LDPE−g−PS)や、ポリプロピレンを主鎖としてスチレン−アクリロニトリル共重合体を側鎖に持つオレフィン系グラフト共重合体(PP−g−AS)などが挙げられる。
本発明においては、これらの中でも特に、ゴムとの接着性および相容性の観点から、スチレン−ブタジエン共重合体、スチレン−ブタジエン−ブチレン−スチレン共重合体およびスチレン−エチレン−ブタジエン−スチレン共重合体を、好適に用いることができる。また、被着ゴムがBR、SBR、NRなどの極性が少ないゴムからなる組成物の場合は、スチレン系ブロック共重合体あるいはその水添化物は、変性などにより極性が強い官能基を持たない方が、相溶性が高くなるので、好ましい。
スチレン系エラストマーは、1種を単独で、または、2種以上を適宜組合わせて用いることができる。
前記カーボンブラックとしては、タイヤ工業において一般的に用いられているSAF、ISAF、HAF、FF、FEF、GPF等が挙げられ、これらのカーボンブラックを単独で用いることも、2種以上を組み合わせて用いることもできる。
カーボンブラックの配合量は、樹脂材料(B)において、オレフィン系重合体(X)の100質量部に対し、0.1〜100質量部、好ましくは1〜30質量部とすることができる。カーボンブラックの配合量が0.1質量部以上になると、本発明のコードが黒に着色され、タイヤなどでは黒色ゴムと色が一致するため、コードが露出したときなどに色ムラがなくなるため好ましい。カーボンブラックの配合量が1質量部以上になると、カーボンブラックによるポリマー補強効果が得られるため好ましい。一方、30質量部超過になるとカーボンブラック配合樹脂が溶融時に流動化し難くなり、紡糸加工時に糸切れが発生するおそれがある。また、100質量部超過になると、相対的にコードのポリマーなどの成分が少なくなることにより、樹脂材料(B)とゴムとの相容性向上効果が低下するので好ましくない。
素材となる熱可塑性樹脂としては、真空乾燥機を用いて乾燥させた、下記表5に記載された芯材および鞘材の樹脂を用いた。
芯成分および鞘成分として、下記表1〜5に示す材料を用いて、芯材用および鞘材用の2台のφ50mmの単軸押出機で、各表中に示す紡糸温度にて、口径が1.0mmの芯鞘型複合紡糸口金を用いて、鞘芯比率が質量比率で4:6となるように吐出量を調整して、紡糸速度90m/分にて溶融紡糸し、98℃の熱水浴で1.5倍となるように延伸して、繊度550dtexの芯鞘型複合モノフィラメントを得た。
各比較例および実施例の供試タイヤのビード部のリムラインの高さ位置で、本発明のコードを含むテスト用のサンプルピースを切り出して、このサンプルピースから掘り起こした繊維コードについて30cm/分の速度でコードを加硫物から剥離させ、剥離後のコードについて、ゴムの付着状態を観察し、下記表6に従いランク付けを行って、ゴム付着率(ゴム付)を確認し、初期接着性として下記表1〜4に表示した。
各比較例および実施例の供試タイヤを、JATMA YEAR BOOK−2015規格の適用リム(標準リム)にリム組みし、25±2℃の室内にて内圧を200kPaに調整してから、24時間放置した後、タイヤの空気圧の再調整を行い、JATMA規格の120%の荷重(荷重564kgf、空気圧200kPa)をタイヤに付加し、速度60km/時で5万kmの距離を直径約3mのドラム上にて連続走行させることで、比較例及び実施例の供試タイヤに「一般的な市街地走行に近い走行条件であるがより高い荷重負荷の条件」で走行時の熱劣化と疲労を入力した。各タイヤのビード部のリムラインの高さ位置で、本発明のコードを含むテスト用のサンプルピースを切り出して、このサンプルピースから掘り起こした繊維コードについて30cm/分の速度でコードを加硫物から剥離させ、剥離後のコードについて、ゴムの付着状態を観察し、下記表6に従いランク付けを行って、ゴム付着率(ゴム付)を確認し、疲労後接着性として下記表1〜4に表示した。
2)BR:ブチルゴム(エクソン社製 商品名:ブロモブチル2255)
3)東海カーボン シースト300
4)加硫助剤(新日本理化製 50S)
5)加硫促進助剤(ハクスイテック製 酸化亜鉛華)
6)老化防止剤:N−(1,3−ジメチルブチル)−N’−p−フェニレンジアミン、大内新興化学工業(株)製、ノクラック6C
7)加硫促進剤:シクロヘキシルベンゾチアジルスルフェンアミド、大内新興化学工業(株)製、CZ
8)細井化学工業(株)製、HK−200−5(5質量%オイル含有粉末硫黄)
1a ビードコア1のタイヤ半径方向外側端部
2 カーカス層
2A カーカスプライの本体部
2B カーカスプライのタイヤ幅方向端部
3 ベルト層
4 補強層
5 ビードフィラー
11 ビード部
12 サイドウォール部
13 トレッド部
Claims (15)
- 芯部が融点150℃以上の高融点樹脂(A)からなり、鞘部が、該高融点樹脂(A)よりも融点の低い樹脂材料(B)からなる芯鞘型の複合繊維よりなるゴム補強用繊維であって、
前記樹脂材料(B)が、オレフィン系重合体(X)と、加硫促進剤(F)と、を含有することを特徴とするゴム補強用繊維。 - 前記樹脂材料(B)が、さらに、相容化剤(E)および充填剤(N)からなる群から選ばれる1種以上を含有する請求項1記載のゴム補強用繊維。
- 前記オレフィン系重合体(X)が、ルイス塩基性官能基を含む付加重合可能なモノマーの含有量が5モル%以下であるオレフィン系重合体(Y)である請求項1記載のゴム補強用繊維。
- 前記オレフィン系重合体(Y)のルイス塩基性官能基が、ピリジル基、N‐置換イミダゾリル基、N‐置換インダゾリル基、ニトリル基、アジド基、N‐置換イミノ基、N,N‐置換アミノ基、N,N‐置換アミノオキシ基、N,N,N‐置換ヒドラジノ基、ニトロソ基、ニトロ基、ニトロオキシ基、フリル基、カルボニル基、チオカルボニル基、アルコキシ基、アルキルオキシカルボニル基、N,N‐置換カルバモイル基、チオアルコキシ基、置換スルフィニル基、置換スルホニル基または置換スルホン酸基である請求項3記載のゴム補強用繊維。
- 前記オレフィン系重合体(X)が、オレフィン系ランダム共重合体(C)および/またはオレフィン系ホモ重合体若しくはオレフィン系共重合体(D)((C)を除く)からなる請求項1記載のゴム補強用繊維。
- 前記オレフィン系重合体(X)が、共役ジエンを含むオレフィン系ランダム共重合体(C2)を含む請求項1記載のゴム補強用繊維。
- 前記加硫促進剤(F)が、ルイス塩基性化合物(F1)、または、チールラジカルを発生できる化合物(F2)である請求項1記載のゴム補強用繊維。
- 前記チールラジカルを発生できる化合物(F2)が、チオウレア類、チアゾール類、スルフェンアミド類、チウラム類、ジチオカルバミン酸類またはキサントゲン酸類の加硫促進剤である請求項7記載のゴム補強用繊維。
- 前記相容化剤(E)が、スチレン単量体を主として連続して配列してなる単独分子鎖を含むスチレン系エラストマーである請求項2記載のゴム補強用繊維。
- 前記充填剤(N)が、カーボンブラックである請求項2記載のゴム補強用繊維。
- 前記樹脂材料(B)が、前記オレフィン系重合体(X)100質量部に対し、前記加硫促進剤(F)を0.05〜20質量部含有する請求項1記載のゴム補強用繊維。
- 前記樹脂材料(B)が、前記オレフィン系重合体(X)100質量部に対し、前記相容化剤(E)および/または充填剤(N)を0.1〜30質量部含有する請求項2記載のゴム補強用繊維。
- 前記オレフィン系重合体(X)100質量部中に、前記共役ジエンを含むオレフィン系ランダム共重合体(C2)が5〜95質量部含まれる請求項6記載のゴム補強用繊維。
- 請求項1記載のゴム補強用繊維よりなる補強材が、ゴム被覆されてなることを特徴とするゴム−繊維複合体。
- 請求項14記載のゴム−繊維複合体からなる補強層を備えることを特徴とする空気入りタイヤ。
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