JP6743700B2 - タイヤ用積層体、タイヤ用インナーライナー材及び空気入りタイヤ - Google Patents
タイヤ用積層体、タイヤ用インナーライナー材及び空気入りタイヤ Download PDFInfo
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- JP6743700B2 JP6743700B2 JP2016550423A JP2016550423A JP6743700B2 JP 6743700 B2 JP6743700 B2 JP 6743700B2 JP 2016550423 A JP2016550423 A JP 2016550423A JP 2016550423 A JP2016550423 A JP 2016550423A JP 6743700 B2 JP6743700 B2 JP 6743700B2
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- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- 239000012990 dithiocarbamate Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Description
(a)少なくとも1種のゴム成分、
(b)下記式(1):
で表される化合物とホルムアルデヒドとの縮合物、
(c)少なくとも1種のメチレンドナー、及び
(d)加硫剤、
を含み、
縮合物(b)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.5〜20質量部の量で存在し、
少なくとも1種のメチレンドナー(c)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.25〜200質量部の量で存在し、
少なくとも1種のメチレンドナー(c)と縮合物(b)の質量比が0.5:1〜10:1であり、
少なくとも1種のゴム成分(a)が、脂肪族不飽和炭化水素側鎖中のビニル量が11モル%超であるゴムを、少なくとも1種のゴム成分(a)の合計量を基準として10質量%〜80質量%の量で含むこと、
を特徴とする積層体が提供される。
本発明によれば、さらに、上記の積層体から成る空気入りタイヤ用インナーライナー材が提供される。
本発明によれば、さらに、上記の積層体から成る空気入りタイヤ用インナーライナー材を含む空気入りタイヤが提供される。
[1]熱可塑性樹脂組成物のフィルムと当該フィルムに積層されたゴム組成物の層とを含むタイヤ用積層体であって、ゴム組成物が、
(a)少なくとも1種のゴム成分、
(b)下記式(1):
で表される化合物とホルムアルデヒドとの縮合物、
(c)少なくとも1種のメチレンドナー、及び
(d)加硫剤、
を含み、
縮合物(b)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.5〜20質量部の量で存在し、
少なくとも1種のメチレンドナー(c)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.25〜200質量部の量で存在し、
少なくとも1種のメチレンドナー(c)と縮合物(b)の質量比が0.5:1〜10:1であり、
少なくとも1種のゴム成分(a)が、脂肪族不飽和炭化水素側鎖中のビニル量が11モル%超であるゴムを、少なくとも1種のゴム成分(a)の合計量を基準として10質量%〜80質量%の量で含むこと、
を特徴とする積層体が提供される。
[2]脂肪族不飽和炭化水素側鎖がビニル基である、上記態様[1]に記載の積層体。
[3]熱可塑性樹脂組成物が、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ナイロン6、ナイロン66、ナイロン11、ナイロン12、ナイロン610、ナイロン612、ナイロン6/66、ナイロンMXD6及びナイロン6Tからなる群から選ばれた少なくとも1種の熱可塑性樹脂を含むことを特徴とする、上記態様[1]又は[2]に記載の積層体。
[4]熱可塑性樹脂組成物が、少なくとも1種の熱可塑性樹脂と当該熱可塑性樹脂中に分散された少なくとも1種のエラストマーとを含み、少なくとも1種の熱可塑性樹脂が、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ナイロン6、ナイロン66、ナイロン11、ナイロン12、ナイロン610、ナイロン612、ナイロン6/66、ナイロンMXD6及びナイロン6Tからなる群から選ばれ、少なくとも1種のエラストマーが、臭素化イソブチレン−p−メチルスチレン共重合体、無水マレイン酸変性エチレン−α−オレフィン共重合体、エチレン−グリシジルメタクリレート共重合体及び無水マレイン酸変性エチレン−エチルアクリレート共重合体からなる群から選ばれる、上記態様[1]又は[2]に記載の積層体。
[5]少なくとも1種のメチレンドナーが、変性エーテル化メチロールメラミン、パラホルムアルデヒド、ヘキサメチレンテトラミン、ペンタメチレンテトラミン及びヘキサメトキシメチルメラミンからなる群から選ばれる、上記態様[1]〜[4]のいずれか1つに記載の積層体。
[6]上記態様[1]〜[5]のいずれか1つに記載の積層体から成る空気入りタイヤ用インナーライナー材。
[7]上記態様[1]〜[5]のいずれか1つの記載の積層体から成る空気入りタイヤ用インナーライナー材を含む空気入りタイヤ。
(a)少なくとも1種のゴム成分、
(b)下記式(1):
で表される化合物とホルムアルデヒドとの縮合物、
(c)少なくとも1種のメチレンドナー、及び
(d)加硫剤、
を含み、
縮合物(b)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.5〜20質量部の量で存在し、
少なくとも1種のメチレンドナー(c)が少なくとも1種のゴム成分(a)の合計量100質量部に対して0.25〜200質量部の量で存在し、
少なくとも1種のメチレンドナー(c)と縮合物(b)の質量比が0.5:1〜10:1であり、
少なくとも1種のゴム成分(a)が、脂肪族不飽和炭化水素側鎖中のビニル量が11モル%超であるゴムを、少なくとも1種のゴム成分(a)の合計量を基準として10質量%〜80質量%の量で含むことを特徴とする。
表1に示す配合比率で原料を配合して熱可塑性樹脂組成物を調製し、その熱可塑性樹脂組成物をインフレーション成形装置で成形し、厚さ0.2mmのフィルムを作製した。作製したフィルムをフィルムAという。
BIMS:臭素化イソブチレン−p−メチルスチレン共重合体(エクソンモービルケミカル社製のExxpro(登録商標)3035)
酸化亜鉛:正同化学工業(株)製の亜鉛華3号
ステアリン酸:千葉脂肪酸(株)製の工業用ステアリン酸
ステアリン酸亜鉛:日油(株)製のステアリン酸亜鉛
熱可塑性樹脂:ナイロン6/66(宇部興産(株)製のUBEナイロン(登録商標)5033B)
変性EEA:アルケア社製のリルサンBESNOTL
可塑剤:大八化学工業(株)製のBM−4
下記の原料を表2に示す配合比率でバンバリーミキサーにより配合し、比較例1〜3及び実施例1〜4のゴム組成物を調製した。
ゴム組成物の原料:
SBR1:日本ゼオン(株)製のNipol(登録商標)1502(1,2−ビニル量:11%)
SBR2:旭化成ケミカルズ(株)製のタフデン(登録商標)1000(1,2−ビニル量:7%)
SBR3:旭化成ケミカルズ(株)製のタフデン(登録商標)2000R(1,2−ビニル量:7%)
SBR4:日本ゼオン(株)製のNipol(登録商標)NS616(1,2−ビニル量:50%)
NR:SIR−20
カーボンブラック:東海カーボン(株)社製シーストV
ステアリン酸:千葉脂肪酸(株)製の工業用ステアリン酸
アロマオイル:昭和シェル石油(株)製のデソレックス3号
酸化亜鉛:正同化学工業(株)製の亜鉛華3号
縮合体:変性レゾルシン・ホルムアルデヒド縮合体(田岡化学工業(株)製のスミカノール620)
メチレンドナー:変性エーテル化メチロールメラミン樹脂(田岡化学工業(株)製のスミカノール507AP)
硫黄:(株)軽井沢精錬所製の5%油展処理硫黄
加硫促進剤:ジ−2−ベンゾチアゾリルスジルフィド(大内新興化学工業(株)製のノクセラーDM)
上記(1)で作製したフィルムAの上に、上記(2)で調製したゴム組成物を0.7mmの厚さで押出積層し積層体を作製した。
作製した積層体について、下記の「剥離強度試験」を行い評価した。評価結果を表2に示す。
[剥離強度試験]
積層体の試料を、加硫後、幅25mmに切断し、その短冊状試験片の剥離強度をJIS−K6256に従い測定した。測定された剥離強度(N/25mm)を、比較例1の剥離強度を100として指数化した。
Claims (7)
- 熱可塑性樹脂組成物のフィルムと当該フィルムに積層されたゴム組成物の層とを含むタイヤ用積層体であって、前記ゴム組成物が、
(a)天然ゴム、スチレンブタジエンゴム、ブタジエンゴム、イソプレンゴム、及びそれらの混合物から成る群から選ばれる少なくとも1種のゴム成分、
(b)下記式(1):
で表される化合物とホルムアルデヒドとの縮合物、
(c)少なくとも1種のメチレンドナー、及び
(d)加硫剤、
を含み、
縮合物(b)が前記少なくとも1種のゴム成分(a)の合計量100質量部に対して0.5〜20質量部の量で存在し、
少なくとも1種のメチレンドナー(c)が前記少なくとも1種のゴム成分(a)の合計量100質量部に対して0.25〜200質量部の量で存在し、
少なくとも1種のメチレンドナー(c)と縮合物(b)の質量比が0.5:1〜10:1であり、
少なくとも1種のゴム成分(a)が、脂肪族不飽和炭化水素側鎖中のビニル量が11モル%超であるゴムを、少なくとも1種のゴム成分(a)の合計量を基準として10質量%〜80質量%の量で含むこと、
を特徴とする、タイヤ用積層体。 - 脂肪族不飽和炭化水素側鎖がビニル基である、請求項1に記載の積層体。
- 熱可塑性樹脂組成物が、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ナイロン6、ナイロン66、ナイロン11、ナイロン12、ナイロン610、ナイロン612、ナイロン6/66、ナイロンMXD6及びナイロン6Tからなる群から選ばれた少なくとも1種の熱可塑性樹脂を含むことを特徴とする、請求項1又は2に記載の積層体。
- 熱可塑性樹脂組成物が、少なくとも1種の熱可塑性樹脂と当該熱可塑性樹脂中に分散された少なくとも1種のエラストマーとを含み、前記少なくとも1種の熱可塑性樹脂が、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ナイロン6、ナイロン66、ナイロン11、ナイロン12、ナイロン610、ナイロン612、ナイロン6/66、ナイロンMXD6及びナイロン6Tからなる群から選ばれ、少なくとも1種のエラストマーが、臭素化イソブチレン−p−メチルスチレン共重合体、無水マレイン酸変性エチレン−α−オレフィン共重合体、エチレン−グリシジルメタクリレート共重合体及び無水マレイン酸変性エチレン−エチルアクリレート共重合体からなる群から選ばれる、請求項1又は2に記載の積層体。
- 少なくとも1種のメチレンドナーが、変性エーテル化メチロールメラミン、パラホルムアルデヒド、ヘキサメチレンテトラミン、ペンタメチレンテトラミン及びヘキサメトキシメチルメラミンからなる群から選ばれる、請求項1〜4のいずれか一項に記載の積層体。
- 請求項1〜5のいずれか一項に記載の積層体から成る空気入りタイヤ用インナーライナー材。
- 請求項1〜5のいずれか一項に記載の積層体から成る空気入りタイヤ用インナーライナー材を含む空気入りタイヤ。
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