JP3868062B2 - Adhesion method between polyparaphenylene benzobisoxazole fiber and chloroprene rubber - Google Patents
Adhesion method between polyparaphenylene benzobisoxazole fiber and chloroprene rubber Download PDFInfo
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- JP3868062B2 JP3868062B2 JP16456697A JP16456697A JP3868062B2 JP 3868062 B2 JP3868062 B2 JP 3868062B2 JP 16456697 A JP16456697 A JP 16456697A JP 16456697 A JP16456697 A JP 16456697A JP 3868062 B2 JP3868062 B2 JP 3868062B2
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- chloroprene rubber
- treatment liquid
- soluble urethane
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- urethane resin
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- 239000000835 fiber Substances 0.000 title claims description 47
- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 17
- -1 polyparaphenylene benzobisoxazole Polymers 0.000 title claims description 6
- 239000007788 liquid Substances 0.000 claims description 36
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 24
- 229920000126 latex Polymers 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000004816 latex Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 208000028659 discharge Diseases 0.000 claims description 10
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000006757 chemical reactions by type Methods 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 5
- 229960001755 resorcinol Drugs 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical group C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Tyre Moulding (AREA)
- Tires In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、空気入りタイヤのベルト層やカーカス層として、又はコンベヤベルト、ホースなどに好適な軽量の繊維強化複合材料（ゴム／コード複合体）を得るのに有利なポリパラフェニレンベンゾビスオキサゾール繊維（ＰＢＯ繊維）とクロロプレンゴム（ＣＲ）との接着方法に関する。
【０００２】
【従来の技術】
クロロプレンゴムは、耐候性、耐油性、耐摩耗性、耐薬品性、耐炎性等に優れているため、近年、天然ゴムに代えてゴム／コード複合体に用いられるようになった。
一方、ヘテロ環含有芳香族ポリマーからなる繊維の中で、ＰＢＯ繊維は、アラミド繊維（芳香族ポリアミド繊維）の約２倍の強度と引張り弾性を有する。このためＰＢＯ繊維をタイヤ、コンベアベルトなどのゴム製品の補強材として使用することができれば、アラミド繊維の場合に比してその繊維の使用量を低減しながらさらに高い補強効果が与えられ、コード／ゴム複合体の軽量化の達成が期待できる。しかしながら、ＰＢＯ繊維はその分子骨格上、ほとんど官能基を有していないため、ゴム、特にクロロプレンゴムと接着させることが困難であった。
【０００３】
【発明が解決しようとする課題】
従って、本発明の目的は、前述の従来技術におけるクロロプレンゴムとＰＢＯ繊維の接着性の問題を解決して、ＰＢＯ繊維と未加硫クロロプレンゴムと一体化加硫して、ＰＢＯ繊維の数々の特長を保持した上で、クロロプレンゴムとの接着性を改良したゴム／コード複合体を製造するための繊維接着方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明に従えば、ＰＢＯ繊維をプラズマ放電処理により表面処理した後、該ＰＢＯ繊維をエポキシ化合物、ビニルピリジン・スチレン・ブタジエン共重合ゴムラテックスおよび熱反応型水溶性ウレタン樹脂からなる第一処理液で処理し、次にレゾルシン、ホルマリン、クロロプレンゴムラテックスおよび熱反応型水溶性ウレタン樹脂からなる第二処理液で処理した後、未加硫クロロプレンゴムと一体化加硫することからなる接着方法であって、前記熱反応型水溶性ウレタン樹脂が、下記一般式（１）に示される、ブロックされたイソシアネート基を一分子中に３個以上有するものであり、前記第２処理液中のレゾルシン、ホルマリン及びクロロプレンゴムラテックス（ＲＦＬ）と前記第２処理液中の熱反応型水溶性ウレタン樹脂（Ｕ 2 ）をＲＦＬ／Ｕ 2 で表した固形分重量比が１００／１５〜１００／４０であることを特徴とするＰＢＯ繊維とクロロプレンゴムとの接着方法が提供される。
【化２】
【０００６】
【発明の実施の形態】
本発明で用いるＰＢＯ繊維は、ジアミノレゾルシンとテレフタル酸クロリドをポリリン酸中で溶液重合して得られるポリマーを湿式紡糸して製造することができる。このＰＢＯ繊維からなるコードとしては、Ｋ＝Ｔ√Ｄ（但し、Ｔはコード１０cm当たりの撚り数、Ｄは総デニール数）で表される撚り係数Ｋが０〜2500の範囲となるように撚りを加えてコードとしたものを適用できる。
【０００７】
本発明において用いる第１処理液は、エポキシ化合物（Ｅ）／ビニルピリジン・スチレン・ブタジエン共重合ゴムラテックス（Ｌ）／熱反応型水溶性ウレタン樹脂（Ｕ）からなる。ここで用いるエポキシ化合物（Ｅ）は、例えばグリシジル基を分子中に１個又は２個以上有する公知のエポキシ化合物、好ましくはグリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテルなどのポリオール系エポキシ化合物である。
【０００８】
また、ビニルピリジン・スチレン・ブタジエン共重合ゴムラテックス（Ｌ）としては、公知のものを用いることができる。
熱反応型水溶性ウレタン樹脂（Ｕ）としては、例えば、下記一般式▲１▼に示されるように、ブロックされたイソシアネート基を一分子中に３個以上有するものを用いる。
【０００９】
【化３】
（ここで式中、Ａは官能価３〜５の有機ポリイソシアネート残基を示し、Ｙは加熱によりイソシアネート基を遊離するブロック剤の残基を示し、Ｚは分子中に少なくとも１個の活性水素原子及び少なくとも一個のアニオン形成性残基を有する化合物の残基を示し、Ｘは２〜４個の活性水素原子を有し、平均分子量が５０００以下の、水酸基を有する化合物（例えば多価アルコール、多価アミン、アミノアルコール、ポリエステルポリオールなど）の残基を示し、ｐ＋ｑは２〜４の整数（但しｑ≧０．２５）で、ｒは２〜４の整数である。）このような熱反応型水溶性ウレタン樹脂の製造方法は、特開昭５８−６３７１６号公報に開示されている。
【００１１】
本発明の第１処理液中のエポキシ化合物（Ｅ）とビニルピリジン・スチレン・ブタジエン共重合ゴムラテックス（Ｌ）および熱反応型水溶性ウレタン樹脂（Ｕ）の固形分重量比Ｅ／（Ｌ＋Ｕ）が１００／１００〜１００／８５０、熱反応型水溶性ウレタン樹脂（Ｕ）とビニルピリジン・スチレン・ブタジエン共重合ラテックス（Ｌ）の固形分重量比が４０／１００〜１４０／１００であるのが効果的な接着を得るためにも好ましい。本発明の第１処理液中に配合される熱反応型水溶性ウレタン樹脂の配合量が少なすぎると接着の低下を引き起こし、また逆に多過ぎるとコードが硬くなり、耐久疲労性低下を引き起こす可能性がある。
【００１２】
本発明に係わる第１処理液は、前記各成分を一般的な方法で混合して調製することができ、必要に応じて分散性を良くするための界面活性剤などを配合することができる。第１処理液によるＰＢＯ繊維の処理方法は一般的な繊維の処理方法と同じく、液中への浸漬、ロール塗布、スプレー噴霧などによることができる。ＰＢＯ繊維の第１処理液の付着量は、好ましく３〜８重量％である。処理されたＰＢＯ繊維コードは、例えば、１００〜１５０℃（好ましくは１００〜１４０℃）の温度で乾燥させた後、更に例えば１６０〜２７０℃の温度で、好ましくは２４０〜２６０℃（さらに好ましくは２２０〜２４０℃）の温度で熱処理する。
【００１３】
このように第１処理液で処理されたＰＢＯ繊維は、次に従来脂肪族ポリアミド繊維とゴムとの接着剤として汎用されているＲＦＬからなる第２処理液で処理される。ここで用いるＲＦＬとしては、従来汎用されているものとすることができ、典型的にはレゾルシン・ホルマリン初期縮合物（ＲＦ）／クロロプレンゴムラテックス（Ｌ）である。
【００１４】
ここで上記ＲＦＬに前記一般式（１）で示した熱反応型水溶性ウレタン樹脂を混合してなる第２処理液で処理することで、接着性がさらに向上する効果がある。つまり上記ＲＦＬ成分に加えて、熱反応型水溶性ウレタン樹脂（Ｕ2）をＲＦＬ／熱反応型水溶性ウレタン樹脂（Ｕ2）＝１００／１５〜１００／４０（重量比）の割合で添加することがより好ましい。熱反応型水溶性ウレタン樹脂の配合量が少なくすぎると接着性の低下を引き起こし、また逆に多すぎるとコードが硬くなり、耐疲労性の低下を引き起こす可能性がある。
【００１５】
第２処理液の処理方法は第１処理液と同じ方法とすることができる。ＰＢＯ繊維への第２処理液付着量は、好ましくは２〜６重量％である。処理されたＰＢＯ繊維は乾燥し（例えば、１００〜１５０℃（好ましくは１００〜１４０℃）の温度で）、さらに例えば１２０℃以下の低温で熱処理する。
このようにして第１処理液及び第２処理液で処理されたＰＢＯ繊維は、加硫可能な未加硫クロロプレンゴムに埋設して一体化して加硫することによりゴム／コード複合体とすることができる。
【００１６】
また、予め既知の方法で繊維表面をプラズマ放電処理したＰＢＯ繊維を本発明に従って、上記処理方法で処理し、未加硫クロロプレンゴムと一体化加硫することで、よりいっそう接着性の向上の効果を得ることができる。プラズマ放電処理には、グロー放電などの低温プラズマ、コロナ放電等がある。このうち、コロナ放電処理は、大気圧中での処理が可能であり、経済的にも有利である。コロナ放電処理したＰＢＯ繊維を本発明に従って処理することで、従来処理法に比べ接着性が大きく向上する。なお、ＰＢＯ繊維のフィラメント表面をコロナ放電処理する方法は、例えば、特開平７−２６４１５号公報、特開平７−１０２４７３号公報などに記載されている。
【００１７】
本発明に従えば、ＰＢＯ繊維は、予め繊維表面をプラズマ放電処理したのちエポキシ化合物、ビニルピリジン・スチレン・ブタジエン共重合ゴムラテックスおよび熱反応型水溶性ウレタン樹脂からなる第１処理液で先ず処理され、次いでＲＦＬ（Ｌはクロロプレンゴムラテックス）と熱反応型水溶性ウレタン樹脂からなる第２処理液で処理されるので、未加硫クロロプレンゴムとの一体化加硫により、クロロプレンゴムとＰＢＯ繊維のコードとの接着性に優れ、ＰＢＯ繊維配合ゴム製品の耐久性が高められる。また、既知の方法により、予めプラズマ放電により表面処理したＰＢＯ繊維を本発明に従って処理することにより、接着性はさらに向上し、配合ゴム製品の耐久性が著しく高められる。
【００１８】
【実施例】
下記の配合内容（重量部）の未加硫ゴム配合物およびＰＢＯ繊維コード（東洋紡績（株）製、1000デニール／２）を用いた。
成分 重量部
クロロプレンゴム １００
亜鉛華 ５
ステアリン酸 ２
カーボンブラック ５０
老化防止剤 １
アロマチック油 ７
硫黄 2.25
加硫促進剤 １
【００１９】
先ず、ＰＢＯ繊維コードを表１および表２に示す配合組成（固形分重量比）の第１処理液に浸漬し、１００℃で１分乾燥後、２４０℃で１分熱処理を施した。さらに表１および表２に示す配合組成の第２処理液に該コードを浸漬し、１００℃で１分乾燥後、１２０℃で１分熱処理を施し処理コードを得た。図１に示すように、処理したコード１は、２５mm幅で３０本を１組として引き揃え、上記の未加硫ゴム配合物のシート２に埋設し、これを２プライ密着し、１５０℃で２０分間加硫して、ゴム／コード複合体３を得た。
【００２０】
次に、剥離試験機で速度５０mm／min で、図１に示すようにプライ間剥離を実施し、剥離後の剥離界面のゴム付着率を目視で測定した。完全にゴムの凝集破壊が生じた場合、ゴム付着率は１００％で接着は最もよい。一方、コード表面が完全に露出した場合ゴム付着率は０％で接着は最も悪い。結果を表１および表２に示す。
【００２１】
【表１】
【表２】
ここで比較例４から１２は、第１処理液の配合比を変えたもの、一方、比較例１３から１６は第２処理液の配合比を変えたものである。なお、ここで用いたエポキシ化合物（Ｅ）はグリセロールジグリシジルエーテル（ナガセ化成製デナコールＥＸ６１４Ｂ）であり、ゴムラテックス（Ｌ）はＶＰラテックス（日本ゼオン製ニポール２５１８ＦＳＡ）であり、熱反応型水溶性ウレタン樹脂（Ｕ及びＵ ２ ）は熱反応型水溶性ウレタン樹脂（第一工業製薬（株）製エラストロンＢＮ−６９）である。実施例１は、予めコード表面をコロナ放電処理したコードを実施例１１と同様な方法で処理したものである。
【００２４】
また、従来例として第１処理液をエポキシ化合物のみとしたもの、比較例４に比し熱反応型水溶性ウレタン樹脂（Ｕ）を除くと共に第２処理液としてＶＰラテックスを用いたもの（比較例１）、比較例４に比し熱反応型水溶性ウレタン樹脂（Ｕ）を除いたもの（比較例２）、比較例４に比しゴムラテックス（Ｌ）を除いたもの（比較例３）を用いて処理し、第２処理液としてＲＦＬで処理したものの結果と併せて表１および表２に示した。ここでＲＦＬは公知であって、ＲＦ／Ｌが１５／１００固形分重量比）である（Ｌはクロロプレンゴムラテックス（ＣＲラテックス））。
【００２５】
表１および表２から明らかなように、本発明に従って予め表面をコロナ放電処理したＰＢＯ繊維を、特定の第１処理液および第２処理液で処理することによって、従来に比して優れた接着力を有するゴム／コード複合体を得ることができ、これによりＰＢＯ繊維使用製品の耐久性を向上させることができる。
【００２６】
【発明の効果】
以上説明したように本発明によれば、予め表面をプラズマ放電処理したＰＢＯ繊維を第１処理液で処理し、次いで第２処理液で処理した後、未加硫クロロプレンゴムと一体化加硫するために、ＰＢＯ繊維のクロロプレンゴムに対する接着性を向上させることができる。
【図面の簡単な説明】
【図１】本発明によって得られるゴム／コード複合体の一例を示す説明図である。
【符号の説明】
１ コード ２ 未加硫ゴム配合物のシート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyparaphenylene benzobisoxazole fiber advantageous for obtaining a lightweight fiber-reinforced composite material (rubber / cord composite) suitable as a belt layer or a carcass layer of a pneumatic tire or as a conveyor belt or a hose. The present invention relates to a method for bonding (PBO fiber) and chloroprene rubber (CR).
[0002]
[Prior art]
Since chloroprene rubber is excellent in weather resistance, oil resistance, abrasion resistance, chemical resistance, flame resistance, and the like, it has recently been used in rubber / cord composites in place of natural rubber.
On the other hand, among the fibers made of a heterocycle-containing aromatic polymer, the PBO fiber has about twice the strength and tensile elasticity of an aramid fiber (aromatic polyamide fiber). Therefore, if the PBO fiber can be used as a reinforcing material for rubber products such as tires and conveyor belts, a higher reinforcing effect can be given while reducing the amount of the fiber used compared to the case of aramid fiber. Achievement of weight reduction of rubber composites can be expected. However, since PBO fibers have almost no functional groups on their molecular skeleton, it has been difficult to bond them to rubber, particularly chloroprene rubber.
[0003]
[Problems to be solved by the invention]
Accordingly, the object of the present invention is to solve the problem of adhesion between chloroprene rubber and PBO fiber in the above-mentioned prior art, and to integrally vulcanize PBO fiber and unvulcanized chloroprene rubber, and to obtain various features of PBO fiber. It is another object of the present invention to provide a fiber bonding method for producing a rubber / cord composite having improved adhesion to chloroprene rubber.
[0004]
[Means for Solving the Problems]
According to the present invention, after PBO fiber is surface-treated by plasma discharge treatment, the PBO fiber is treated with a first treatment liquid comprising an epoxy compound, a vinylpyridine / styrene / butadiene copolymer rubber latex, and a heat-reactive water-soluble urethane resin. An adhesive method comprising: treating, then treating with a second treatment liquid comprising resorcin, formalin, chloroprene rubber latex and a heat-reactive water-soluble urethane resin, and then integrally vulcanizing with unvulcanized chloroprene rubber. The heat-reactive water-soluble urethane resin has three or more blocked isocyanate groups represented by the following general formula (1) in one molecule, and resorcin, formalin and chloroprene rubber latex (RFL) and heat reaction type water-soluble urethane resin of the second treatment liquid in (U 2) R Method of bonding PBO fibers and chloroprene rubber, wherein the solid weight ratio, expressed in L / U 2 is 100 / 15-100 / 40, is provided.
[Chemical 2]
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The PBO fiber used in the present invention can be produced by wet spinning a polymer obtained by solution polymerization of diaminoresorcin and terephthalic acid chloride in polyphosphoric acid. The cord made of this PBO fiber is twisted so that the twist coefficient K represented by K = T√D (where T is the number of twists per 10 cm of the cord and D is the total number of deniers) is in the range of 0 to 2500. Applicable code can be applied.
[0007]
The first treatment liquid used in the present invention is composed of epoxy compound (E) / vinylpyridine / styrene / butadiene copolymer rubber latex (L) / thermal reaction type water-soluble urethane resin (U). The epoxy compound (E) used here is, for example, a known epoxy compound having one or more glycidyl groups in the molecule, preferably a polyol system such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. It is an epoxy compound.
[0008]
As the vinylpyridine / styrene / butadiene copolymer rubber latex (L), a known one can be used.
As the heat-reactive water-soluble urethane resin (U), for example, as shown in the following general formula (1), one having 3 or more blocked isocyanate groups in one molecule is used.
[0009]
[Chemical 3]
(Wherein A represents an organic polyisocyanate residue having a functionality of 3 to 5, Y represents a residue of a blocking agent which liberates an isocyanate group by heating, and Z represents at least one active hydrogen in the molecule) A residue of a compound having an atom and at least one anion-forming residue, wherein X is a compound having a hydroxyl group having 2 to 4 active hydrogen atoms and an average molecular weight of 5000 or less (for example, a polyhydric alcohol, A residue of polyvalent amine, amino alcohol, polyester polyol, etc.), p + q is an integer of 2 to 4 (where q ≧ 0.25), and r is an integer of 2 to 4.) Such thermal reaction A method for producing a mold-type water-soluble urethane resin is disclosed in JP-A-58-63716 .
[0011]
The solid content weight ratio E / (L + U) of the epoxy compound (E), the vinylpyridine / styrene / butadiene copolymer rubber latex (L) and the heat-reactive water-soluble urethane resin (U) in the first treatment liquid of the present invention is It is effective that the solid content weight ratio of the heat-reactive water-soluble urethane resin (U) and the vinylpyridine / styrene / butadiene copolymer latex (L) is 40/100 to 140/100. It is also preferable for obtaining a good adhesion. If the blending amount of the heat-reactive water-soluble urethane resin blended in the first treatment liquid of the present invention is too small, it may cause a decrease in adhesion, and conversely if too large, the cord becomes hard and may cause a decrease in durability fatigue. There is sex.
[0012]
The 1st process liquid concerning this invention can mix and prepare the said each component by a general method, and can mix | blend surfactant etc. for improving dispersibility as needed. The PBO fiber treatment method using the first treatment liquid can be performed by immersion in the liquid, roll coating, spray spraying, or the like, as in the general fiber treatment method. The adhesion amount of the first treatment liquid of PBO fiber is preferably 3 to 8% by weight. The treated PBO fiber cord is, for example, dried at a temperature of 100 to 150 ° C. (preferably 100 to 140 ° C.), and further at a temperature of 160 to 270 ° C., preferably 240 to 260 ° C. (more preferably Heat treatment at a temperature of 220-240 ° C.
[0013]
The PBO fiber thus treated with the first treatment liquid is then treated with a second treatment liquid made of RFL, which has been conventionally used as an adhesive between aliphatic polyamide fibers and rubber. The RFL used here may be one conventionally used and is typically resorcin / formalin precondensate (RF) / chloroprene rubber latex (L).
[0014]
Here, the treatment with the second treatment liquid obtained by mixing the RFL with the heat-reactive water-soluble urethane resin represented by the general formula (1) has an effect of further improving the adhesiveness. That in addition to the above RFL component is added at a rate of thermal reaction type water-soluble urethane resin (U 2) a RFL / thermal reaction type water-soluble urethane resin (U 2) = 100/15 ~100 / 40 ( weight ratio) It is more preferable. If the blending amount of the heat-reactive water-soluble urethane resin is too small, the adhesiveness is lowered. On the other hand, if it is too much, the cord becomes hard and the fatigue resistance may be lowered.
[0015]
The treatment method of the second treatment liquid can be the same method as the first treatment liquid. The amount of the second treatment liquid attached to the PBO fiber is preferably 2 to 6% by weight. The treated PBO fiber is dried (for example, at a temperature of 100 to 150 ° C. (preferably 100 to 140 ° C.)), and further heat-treated at a low temperature of, for example, 120 ° C. or less.
The PBO fibers thus treated with the first treatment liquid and the second treatment liquid are embedded in a vulcanizable unvulcanized chloroprene rubber and integrally vulcanized to form a rubber / cord composite. Can do.
[0016]
Further, the PBO fiber whose fiber surface has been subjected to plasma discharge treatment by a known method in advance is treated by the above treatment method according to the present invention, and is integrally vulcanized with unvulcanized chloroprene rubber, thereby further improving the adhesiveness. Can be obtained. Plasma discharge treatment includes low temperature plasma such as glow discharge, corona discharge and the like. Among these, the corona discharge treatment can be carried out at atmospheric pressure, and is economically advantageous. By treating the PBO fiber subjected to corona discharge treatment according to the present invention, the adhesiveness is greatly improved as compared with the conventional treatment method. Incidentally, methods for subjecting the filament surface of the PBO fiber to corona discharge are described in, for example, JP-A-7-26415 and JP-A-7-102473.
[0017]
According to the present invention, the PBO fiber is first treated with a first treatment liquid comprising an epoxy compound, a vinylpyridine / styrene / butadiene copolymer rubber latex and a heat-reactive water-soluble urethane resin after the fiber surface has been subjected to plasma discharge treatment in advance. Then, since it is treated with a second treatment liquid comprising RFL (L is chloroprene rubber latex ) and a heat-reactive water-soluble urethane resin, the cord of chloroprene rubber and PBO fiber is integrated by vulcanization with unvulcanized chloroprene rubber. The durability of the PBO fiber compounded rubber product is enhanced. Further, by treating the PBO fiber that has been surface-treated by plasma discharge in accordance with the present invention by a known method, the adhesion is further improved, and the durability of the compounded rubber product is remarkably enhanced.
[0018]
【Example】
An unvulcanized rubber compound and PBO fiber cord (Toyobo Co., Ltd., 1000 denier / 2) having the following compounding contents (parts by weight) were used.
Ingredient weight parts Chloroprene rubber 100
Zinc flower 5
Carbon black 50
Anti-aging agent 1
Aromatic oil 7
Sulfur 2.25
Vulcanization accelerator 1
[0019]
First, the PBO fiber cord was immersed in a first treatment liquid having a composition (solid weight ratio) shown in Tables 1 and 2, dried at 100 ° C. for 1 minute, and then heat treated at 240 ° C. for 1 minute. Further, the cord was immersed in a second treatment liquid having the composition shown in Table 1 and Table 2, dried at 100 ° C. for 1 minute, and then heat treated at 120 ° C. for 1 minute to obtain a treated cord. As shown in FIG. 1, the treated cord 1 has a 25 mm width, 30 wires are arranged as a set, embedded in a
[0020]
Next, peeling between plies was carried out as shown in FIG. 1 at a speed of 50 mm / min with a peeling tester, and the rubber adhesion rate at the peeling interface after peeling was measured visually. When complete cohesive failure of rubber occurs, the adhesion rate is the best with a rubber adhesion rate of 100%. On the other hand, when the cord surface is completely exposed, the rubber adhesion rate is 0% and the adhesion is the worst. The results are shown in Tables 1 and 2.
[0021]
[Table 1]
[Table 2]
Here, Comparative Examples 4 to 12 were obtained by changing the blending ratio of the first treatment liquid, while Comparative Examples 13 to 16 were obtained by changing the blending ratio of the second treatment liquid. The epoxy compound (E) used here is glycerol diglycidyl ether (Denacol EX614B manufactured by Nagase Kasei), the rubber latex (L) is VP latex (Nipol 2518FSA manufactured by Nippon Zeon Co., Ltd.), and a heat-reactive water-soluble urethane. The resins (U and U 2 ) are heat-reactive water-soluble urethane resins (Elastolone BN-69 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). In Example 1 , a cord obtained by subjecting the cord surface in advance to corona discharge treatment was treated in the same manner as in Example 11.
[0024]
Further, as a conventional example, the first treatment liquid is made only of an epoxy compound, and compared with Comparative Example 4 , a heat-reactive water-soluble urethane resin (U) is removed and VP latex is used as a second treatment liquid (Comparative Example). 1), excluding the thermal reaction type water-soluble urethane resin (U) than in Comparative example 4 (Comparative example 2), excluding the rubber latex (L) than in Comparative example 4 (Comparative example 3) Table 1 and Table 2 together with the results of the treatment with RFL as the second treatment liquid. Here, RFL is known and RF / L is 15/100 solids weight ratio) (L is chloroprene rubber latex (CR latex)).
[0025]
As is apparent from Tables 1 and 2, the PBO fiber whose surface has been previously subjected to corona discharge treatment according to the present invention is treated with a specific first treatment liquid and a second treatment liquid, thereby providing superior adhesion as compared with the prior art. A rubber / cord composite having strength can be obtained, whereby the durability of the product using PBO fibers can be improved.
[0026]
【The invention's effect】
As described above, according to the present invention, the PBO fiber whose surface has been subjected to plasma discharge treatment in advance is treated with the first treatment liquid, then treated with the second treatment liquid, and then integrally vulcanized with the unvulcanized chloroprene rubber. Therefore, the adhesiveness of PBO fibers to chloroprene rubber can be improved.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing an example of a rubber / cord composite obtained by the present invention.
[Explanation of symbols]
1
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16456697A JP3868062B2 (en) | 1997-06-20 | 1997-06-20 | Adhesion method between polyparaphenylene benzobisoxazole fiber and chloroprene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16456697A JP3868062B2 (en) | 1997-06-20 | 1997-06-20 | Adhesion method between polyparaphenylene benzobisoxazole fiber and chloroprene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1112370A JPH1112370A (en) | 1999-01-19 |
| JP3868062B2 true JP3868062B2 (en) | 2007-01-17 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16456697A Expired - Fee Related JP3868062B2 (en) | 1997-06-20 | 1997-06-20 | Adhesion method between polyparaphenylene benzobisoxazole fiber and chloroprene rubber |
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| Country | Link |
|---|---|
| JP (1) | JP3868062B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3879849A4 (en) * | 2018-11-06 | 2022-08-10 | Yamaha Corporation | Speaker diaphragm |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6908676B2 (en) | 2001-01-25 | 2005-06-21 | Unitta Company | Transmission belt and method of treatment for bonding with poly-p-phenylene benzobisoxazole fiber |
| WO2015031226A1 (en) * | 2013-08-28 | 2015-03-05 | E. I. Du Pont De Nemours And Company | Fibrous cord and method of making |
| DE102017222896A1 (en) * | 2017-12-15 | 2019-07-25 | Continental Reifen Deutschland Gmbh | Hybrid cord for use as a strength carrier in a belt bandage of a pneumatic vehicle tire, method for its production and use |
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1997
- 1997-06-20 JP JP16456697A patent/JP3868062B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3879849A4 (en) * | 2018-11-06 | 2022-08-10 | Yamaha Corporation | Speaker diaphragm |
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| Publication number | Publication date |
|---|---|
| JPH1112370A (en) | 1999-01-19 |
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