JPH05229033A - Yarn prepreg and production of tire using the same - Google Patents
Yarn prepreg and production of tire using the sameInfo
- Publication number
- JPH05229033A JPH05229033A JP4034821A JP3482192A JPH05229033A JP H05229033 A JPH05229033 A JP H05229033A JP 4034821 A JP4034821 A JP 4034821A JP 3482192 A JP3482192 A JP 3482192A JP H05229033 A JPH05229033 A JP H05229033A
- Authority
- JP
- Japan
- Prior art keywords
- yarn
- fiber
- weight
- tire
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000835 fiber Substances 0.000 claims abstract description 44
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000005060 rubber Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 229920003235 aromatic polyamide Polymers 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 abstract description 29
- 229920000647 polyepoxide Polymers 0.000 abstract description 29
- 238000005470 impregnation Methods 0.000 abstract description 7
- 238000010008 shearing Methods 0.000 abstract description 5
- 239000011342 resin composition Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 17
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 229920000561 Twaron Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- ACEXADJQHUQBLM-UHFFFAOYSA-N 1,1-dichloro-3-phenylurea Chemical class ClN(Cl)C(=O)NC1=CC=CC=C1 ACEXADJQHUQBLM-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LHXNVCCLDTYJGT-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)propan-2-ol Chemical compound CC(O)COCC1CO1 LHXNVCCLDTYJGT-UHFFFAOYSA-N 0.000 description 1
- KXHDZOYDQKKBAD-UHFFFAOYSA-N 1-methylcyclohexa-2,4-diene-1,2-diamine Chemical compound CC1(N)CC=CC=C1N KXHDZOYDQKKBAD-UHFFFAOYSA-N 0.000 description 1
- VUWRXQGCYUPIFW-UHFFFAOYSA-N 2,4,6-tris(oxiran-2-ylmethyl)-1,3,5-triazine Chemical compound N=1C(CC2OC2)=NC(CC2OC2)=NC=1CC1CO1 VUWRXQGCYUPIFW-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- TYJBGRITOIMGRY-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethyl)cyclohexyl]propan-2-yl]cyclohexyl]methyl]oxirane Chemical compound C1CC(CC2OC2)CCC1C(C)(C)C(CC1)CCC1CC1CO1 TYJBGRITOIMGRY-UHFFFAOYSA-N 0.000 description 1
- HCPJEHJGFKWRFM-UHFFFAOYSA-N 2-amino-5-methylphenol Chemical compound CC1=CC=C(N)C(O)=C1 HCPJEHJGFKWRFM-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
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- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Tyre Moulding (AREA)
- Tires In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はタイヤ補強材及びそれを
用いたタイヤの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tire reinforcing material and a tire manufacturing method using the same.
【０００２】[0002]
【従来の技術】タイヤには耐摩耗性、耐高速走行性及び
操搬安定性に加えて省エネルギー化のための軽量化が要
求されている。軽量化を達成するために高強度かつ高弾
性を有する有機物繊維、なかでも芳香族ポリアラミド繊
維の応用が検討されてきた。特にポリパラフェニレンテ
レフタルアミド繊維（以下ＰＰＴＡ繊維と略称すること
がある）が主として検討の対象となってきた。2. Description of the Related Art Tires are required to be lightweight in order to save energy in addition to wear resistance, high speed running resistance, and handling stability. In order to achieve weight reduction, application of organic fibers having high strength and high elasticity, particularly aromatic polyaramid fibers, has been studied. In particular, polyparaphenylene terephthalamide fiber (hereinafter sometimes abbreviated as PPTA fiber) has been mainly the subject of study.
【０００３】当初は小型トラックのタイヤのカーカス部
に使用されるスチールコードの代替としてＰＰＴＡ繊維
製コードが研究された。ＰＰＴＡ繊維製コードはゴムと
の接着性を向上させるため、ＰＰＴＡ繊維ヤーンにレゾ
ルシン・ホルマリン樹脂液（以下ＲＦＬと略称すること
がある）とゴムエマルジョン液の混合物等を含浸する。
しかし、該混合物はコードの内部までは含浸されず表層
だけが接着剤で被覆される。この結果、ＰＰＴＡ繊維製
コードは切断時にフライ（ケバ）と呼ばれる繊維のほぐ
れが生じる。その結果、カーカス部を形成するプライの
端面は、生じたフライのためゴムとの接着性が不良とな
り易いという欠点があった。Initially, PPTA fiber cords were studied as an alternative to the steel cords used in the carcass portion of small truck tires. In order to improve the adhesion to the rubber, the PPTA fiber cord impregnates the PPTA fiber yarn with a mixture of a resorcin-formalin resin solution (hereinafter sometimes abbreviated as RFL) and a rubber emulsion solution.
However, the mixture is not impregnated to the inside of the cord, and only the surface layer is covered with the adhesive. As a result, when the PPTA fiber cord is cut, fibers are loosened, which is called fly. As a result, there is a drawback that the end surface of the ply forming the carcass portion is likely to have poor adhesion to rubber due to the generated fly.
【０００４】最近では、ＰＰＴＡ繊維は特開昭６３−１
３４３１０号公報に記載されているように乗用車のラジ
アルタイヤのベルト部のスチールコード代替としても検
討されている。該公報には、ＰＰＴＡ繊維ヤーンをエポ
キシ樹脂組成物で含浸して熱硬化したコードをさらにＲ
ＦＬ／ゴムエマルジョン処理した後、タイヤのベルト部
の補強材として使用することが提案されている。Recently, PPTA fibers have been disclosed in JP-A-63-1.
As described in Japanese Patent No. 34310, it is also considered as a substitute for a steel cord of a belt portion of a radial tire of a passenger car. In this publication, a cord obtained by impregnating PPTA fiber yarn with an epoxy resin composition and thermosetting is further described in R
It has been proposed to use it as a reinforcing material for the belt portion of a tire after FL / rubber emulsion treatment.
【０００５】しかし、従来のコードは前述のように樹脂
の含浸が不十分な場合、内部の繊維は単に細かいフィラ
メントの束となっているだけなので曲げ剛性が不十分に
なり易く、カーカス部と異なり特に曲げ剛性を要求され
るベルト部のコードとして用いるには問題が残されてい
た。また、繊度が１００００ｄｔｅｘを越えるヤーンを
用いたコードでは、せん断力が作用してゴム破壊の原因
となる可能性が高いという問題もある。However, in the conventional cord, when the resin is not sufficiently impregnated as described above, the internal fiber is simply a bundle of fine filaments, so that the bending rigidity tends to be insufficient, which is different from the carcass portion. In particular, there has been a problem in using it as a cord for a belt portion that requires bending rigidity. Further, a cord using a yarn having a fineness of more than 10000 dtex has a problem that shearing force is likely to act and cause rubber breakage.
【０００６】一方、特開平３−１５１２２９号公報に
は、繊度３００〜１４００ｄｔｅｘのＰＰＴＡ繊維ヤー
ンをエポキシ樹脂組成物で含浸して熱硬化したコードを
タイヤのベルト部、カーカス部の補強材として使用する
ことが提案されている。しかし、繊度が低い場合でも、
カーカス部用補強材として用いられるときは曲率が小さ
いのでせん断力が問題となる可能性があり、実用性の観
点からは不安がある。On the other hand, in JP-A-3-151229, a cord obtained by impregnating a PPTA fiber yarn having a fineness of 300 to 1400 dtex with an epoxy resin composition and thermosetting is used as a reinforcing material for a belt portion and a carcass portion of a tire. Is proposed. However, even if the fineness is low,
Since it has a small curvature when used as a reinforcing material for a carcass portion, shearing force may be a problem, which is uncertain from the viewpoint of practicality.
【０００７】また、カーカスプライは加工時にビード部
で折り返されるが、エポキシ樹脂組成物で含浸・熱硬化
されたＰＰＴＡ繊維コードは加工が難しく、より加工性
の優れた材料が求められていた。さらにＰＰＴＡ繊維コ
ードを用いる場合は、ＲＦＬ／ゴムエマルジョン液処理
は必須となっており、その結果、製造工程が複雑化し経
済性が低下するので、製造工程の簡略化が望まれてい
た。Further, the carcass ply is folded back at the bead portion during processing, but the PPTA fiber cord impregnated with the epoxy resin composition and thermoset is difficult to process, and a material having better processability has been demanded. Further, when the PPTA fiber cord is used, the RFL / rubber emulsion liquid treatment is indispensable, and as a result, the manufacturing process becomes complicated and the economical efficiency is lowered. Therefore, simplification of the manufacturing process has been desired.
【０００８】[0008]
【発明が解決しようとする課題】本発明は前述した問題
を解決しようとするものである。すなわち、タイヤ製造
時のＰＰＴＡ繊維コードの加工性が良好であり、ゴムと
繊維コードの接着性と強度に優れたタイヤを、簡素化さ
れた工程で製造しようとするものである。The present invention is intended to solve the above-mentioned problems. That is, it is intended to manufacture a tire having good workability of the PPTA fiber cord at the time of manufacturing the tire and having excellent adhesion and strength between the rubber and the fiber cord in a simplified process.
【０００９】[0009]
【課題を解決するための手段】本発明は芳香族ポリアラ
ミド繊維からなるヤーン５０〜８０重量％に熱硬化性樹
脂２０〜５０重量％を含浸してなることを特徴とする未
加硫ゴムシート積層用のヤーンプリプレグ、及び該ヤー
ンプリプレグを未加硫ゴムシートに積層して加熱する工
程を含むことを特徴とするタイヤの製造方法に関する。DISCLOSURE OF THE INVENTION The present invention is characterized in that 50 to 80% by weight of a yarn made of aromatic polyaramid fiber is impregnated with 20 to 50% by weight of a thermosetting resin. The present invention relates to a yarn prepreg for use in a tire, and a method for manufacturing a tire, comprising a step of laminating the yarn prepreg on an unvulcanized rubber sheet and heating the laminated sheet.
【００１０】以下、本発明について詳しく説明する。本
発明に用いられる芳香族ポリアラミド繊維としては、ポ
リパラフェニレンテレフタルアミド繊維及び３，４’−
オキシジフェニルテレフタルアミド・パラフェニレンテ
レフタルアミド共重縮合体繊維等の全芳香族ポリアミド
繊維が挙げられる。The present invention will be described in detail below. Examples of the aromatic polyaramid fiber used in the present invention include polyparaphenylene terephthalamide fiber and 3,4′-
Examples include wholly aromatic polyamide fibers such as oxydiphenyl terephthalamide / paraphenylene terephthalamide copolycondensate fibers.
【００１１】芳香族ポリアラミド繊維のヤーンの繊度は
目的とするタイヤの種類や補強部位によって選ばれ、好
ましくは２００〜１００００ｄｔｅｘ、含浸性や前記し
たせん断力の問題からより好ましくは３００〜３５００
ｄｔｅｘである。The fineness of the yarn of the aromatic polyaramid fiber is selected according to the type of the target tire and the reinforcing portion, and is preferably 200 to 10000 dtex, more preferably 300 to 3500 in view of the impregnation property and the shearing force.
It is dtex.
【００１２】本発明に用いる芳香族ポリアラミド繊維ヤ
ーンは１ｍ当たり５〜１５０回の撚りをかけることが好
ましい。撚りをかけないものまたは４回以下の撚りでは
曲率の小さい部分にヤーンプリプレグを巻き付けたと
き、繊維が無秩序に押し拡げられて蛇行し易くなる。そ
の結果として引っ張り強度等の物性の低下をきたすこと
がある。撚りが１５０回を越えると、ヤーンプリプレグ
の巻き付けの下地への密着性が不良となる。また、撚り
のため耐疲労性は良くなるものの引っ張り強度は低下す
るという欠点が生じる。The aromatic polyaramid fiber yarn used in the present invention is preferably twisted 5 to 150 times per 1 m. When the yarn prepreg is wound around a portion having a small curvature without twisting or twisting 4 times or less, the fibers are randomly spread and tend to meander. As a result, physical properties such as tensile strength may be deteriorated. If the twist exceeds 150 times, the adhesion of the yarn prepreg to the base on which the yarn is wound becomes poor. In addition, the twisting improves fatigue resistance but reduces tensile strength.
【００１３】撚りの付与は熱硬化性樹脂の含浸前あるい
は含浸後のいずれでもよく、また前後２段階で行っても
良い。撚りをかける方法は特に限定されず、リング式精
紡機を用いる等公知の方法を用いることができる。The twist may be imparted either before or after impregnation with the thermosetting resin, or in two steps before and after. The method of twisting is not particularly limited, and a known method such as using a ring type spinning machine can be used.
【００１４】ヤーンプリプレグの芳香族ポリアラミド繊
維の含有量は５０〜８０重量％である。繊維含有量が５
０重量％未満では十分な強度や剛性が得られにく、８０
重量％を越えると熱硬化性樹脂の含浸が不十分となり、
加工性や接着性に悪影響がでてくる。The content of aromatic polyaramid fiber in the yarn prepreg is 50 to 80% by weight. Fiber content is 5
If it is less than 0% by weight, it is difficult to obtain sufficient strength and rigidity.
If the content exceeds 10% by weight, the thermosetting resin impregnation becomes insufficient,
Workability and adhesiveness are adversely affected.
【００１５】本発明に用いられる熱硬化性樹脂としては
エポキシ樹脂及びその組成物を用いことができる。エポ
キシ樹脂組成物の粘度は６０℃で１００〜２００００ポ
イズの範囲が好ましい。１００ポイズ未満では、粘着性
（以下タックと称することがある）が高くなり過ぎ、ヤ
ーンプリプレグの取扱い性が悪くなり、２００００ポイ
ズを越えるとエポキシ樹脂組成物自体の取扱い性が低下
する。As the thermosetting resin used in the present invention, an epoxy resin and its composition can be used. The viscosity of the epoxy resin composition is preferably 100 to 20000 poise at 60 ° C. If it is less than 100 poise, the tackiness (hereinafter sometimes referred to as tack) becomes too high, and the handleability of the yarn prepreg deteriorates. If it exceeds 20,000 poise, the handleability of the epoxy resin composition itself deteriorates.
【００１６】エポキシ樹脂としては一分子中にエポキシ
基を二個以上有するものを単独または二種以上混合して
使用することができる。また、一分子中にエポキシ基を
一個有するものを反応性希釈剤として併用することがで
きる。As the epoxy resin, one having two or more epoxy groups in one molecule can be used alone or in combination of two or more kinds. Further, one having one epoxy group in one molecule can be used together as a reactive diluent.
【００１７】特に耐熱性を重視する場合には一分子中に
三個以上のエポキシ基を有するエポキシ樹脂を用いるの
が望ましい。これらのエポキシ樹脂を例示すると、ｐ−
アミノフェノール、ｍ−アミノフェノール、４−アミノ
−ｍ−クレゾール、６−アミノ−ｍ−クレゾール、４，
４’−ジアミノジフェニルメタン、３，３’−ジアミノ
ジフェニルメタン、４，４’−ジアミノジフェニルエー
テル、３，４’−ジアミノジフェニルエーテル、１，４
−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビ
ス（３−アミノフェノキシ）ベンゼン、１，４−ビス
（３−アミノフェノキシ）ベンゼン、１，３−ビス（４
−アミノフェノキシベンゼン、１，３−ビス（３−アミ
ノフェノキシ）ベンゼン、２，２−ビス（４−アミノフ
ェノキシフェニル）プロパン、ｐ−フェニレンジアミ
ン、ｍ−フェニレンジアミン、２，４−トルエンジアミ
ン、２，６−トルエンジアミン、ｐ−キシリレンジアミ
ン、ｍ−キシリレンジアミン、１，４−シクロヘキサン
−ビス（メチルアミン）、１，３−シクロヘキサン−ビ
ス（メチルアミン）等から誘導されるアミン系エポキシ
樹脂、フェノール、ｏ−クレゾール、ｍ−クレゾール、
ｐ−クレゾール等のフェノール類とホルムアルデヒドの
反応生成物であるノボラック樹脂から誘導されるノボラ
ック系エポキシ樹脂、フロログリシン、トリス−（４−
ヒドロキシフェニル）メタン、１，１，２，２−テトラ
キス（４−ヒドロキシフェニル）エタン、ビス〔α−
（ジヒドロキシフェニル）−α−メチルエチル〕ベンゼ
ン等の三価以上のフェノール類から誘導されるグリシジ
ルエーテル化合物、その他、トリグリシジルイソシアヌ
レート、２，４，６−トリグリシジル−ｓ−トリアジ
ン、またはこれらのゴム、ウレタン変性化合物等があ
り、これらのエポキシ樹脂の一種または二種以上が使用
されるが、これらに限定されるものではない。Especially when importance is attached to heat resistance, it is desirable to use an epoxy resin having three or more epoxy groups in one molecule. Examples of these epoxy resins include p-
Aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4
-Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxybenzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2 Amine-based epoxy resin derived from 1,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 1,3-cyclohexane-bis (methylamine), etc. , Phenol, o-cresol, m-cresol,
A novolac-based epoxy resin derived from a novolac resin which is a reaction product of formaldehyde with phenols such as p-cresol, phloroglysin, tris- (4-
Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, bis [α-
Glycidyl ether compounds derived from trihydric or higher phenols such as (dihydroxyphenyl) -α-methylethyl] benzene, triglycidyl isocyanurate, 2,4,6-triglycidyl-s-triazine, or these There are rubber, urethane-modified compounds, and the like, and one or more of these epoxy resins are used, but not limited thereto.
【００１８】一分子中に二個のエポキシ基を有するエポ
キシ樹脂を例示すると、ビスフェノールＡ、ビスフェノ
ールＦ、ビスフェノールＡＤ、ハイドロキノン、レゾル
シン等の二価フェノール類またはテトラブロムビスフェ
ノールＡ等のハロゲン化ビスフェノール類から誘導され
るジグリシジルエーテル化合物、ｐ−オキシ安息香酸、
ｍ−オキシ安息香酸、テレフタル酸、イソフタル酸等の
芳香族カルボン酸から誘導されるグリシジルエステル系
化合物、５，５−ジメチル・ヒダントイン等から誘導さ
れるヒダントイン系エポキシ樹脂、２，２−ビス（３，
４−エポキシシクロヘキシル）プロパン、２，２−ビス
〔４−（２，３−エポキシプロピル）シクロヘキシル〕
プロパン、ビニルシクロヘキセンジオキサイド、３，４
−エポキシシクロヘキシルメチル−３，４−エポキシシ
クロヘキサンカルボキシレート等の脂環式エポキシ樹
脂、その他ネオペンチルグリコールジグリシジルエーテ
ル、プロピレングリコールグリシジルエーテル、Ｎ，Ｎ
−ジグリシジルアニリン等がある。Examples of epoxy resins having two epoxy groups in one molecule include dihydric phenols such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone and resorcin, or halogenated bisphenols such as tetrabromobisphenol A. Derived diglycidyl ether compound, p-oxybenzoic acid,
Glycidyl ester-based compounds derived from aromatic carboxylic acids such as m-oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin-based epoxy resins derived from 5,5-dimethylhydantoin, and 2,2-bis (3 ，
4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl]
Propane, vinylcyclohexenedioxide, 3,4
Alicyclic epoxy resin such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, other neopentyl glycol diglycidyl ether, propylene glycol glycidyl ether, N, N
-Diglycidyl aniline and the like.
【００１９】本発明に用いられるエポキシ樹脂組成物に
は硬化剤を通常量使用することができる。硬化剤を例示
すると、ジシアンジアミド、３，３’−ジアミノジフェ
ニルスルホン、４，４’−ジアミノジフェニルスルホ
ン、ジアミノジフェニルメタン、ビスフェノールＳ、ビ
スフェノールＡ、テトラメチルグアナジン、フェノール
ノボラック樹脂、クレゾールノボラック樹脂、芳香族ア
ミン、脂肪族アミン、イミダゾール誘導体、酸無水物、
三弗化ホウ素錯体等を挙げることができる。A curing agent may be used in a usual amount in the epoxy resin composition used in the present invention. Examples of the curing agent include dicyandiamide, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, diaminodiphenylmethane, bisphenol S, bisphenol A, tetramethylguanadine, phenol novolac resin, cresol novolac resin, and aroma. Group amine, aliphatic amine, imidazole derivative, acid anhydride,
Examples thereof include boron trifluoride complex.
【００２０】特にシェルフライフに優れ、かつ１２０℃
程度で硬化可能な硬化剤としてはジシアンジアミドが適
している。ジシアンジアミドはエポキシ樹脂１００重量
部当たり３〜２５重量部使用される。また、芳香族アミ
ン系の硬化剤はエポキシ基１モルに対して活性水素当量
が０．７〜１．１モルとなるよう配合される。Particularly excellent shelf life and 120 ° C.
Dicyandiamide is suitable as a curing agent that can be cured to some extent. Dicyandiamide is used in an amount of 3 to 25 parts by weight per 100 parts by weight of the epoxy resin. Further, the aromatic amine-based curing agent is blended so that the active hydrogen equivalent is 0.7 to 1.1 mol per 1 mol of the epoxy group.
【００２１】本発明において、エポキシ樹脂組成物の硬
化を促進するために、公知の促進剤を用いてもよい。例
えば、尿素誘導体やイミダゾール誘導体、三弗化ホウ素
のアミン錯体、三級アミン、三級アミンのカルボン酸塩
等が挙げられる。なかでも、１２０℃程度の低温硬化性
並びにシェルフライフの点では、ジクロロフェニル−
１，１−ジメチルウレアのごとき尿素誘導体がもっとも
優れている。In the present invention, known accelerators may be used to accelerate the curing of the epoxy resin composition. Examples thereof include urea derivatives, imidazole derivatives, boron trifluoride amine complexes, tertiary amines, and tertiary amine carboxylates. Among them, in view of low temperature curability at about 120 ° C and shelf life, dichlorophenyl-
Urea derivatives such as 1,1-dimethylurea are the best.
【００２２】本発明において、エポキシ樹脂組成物に特
定の無機充填材を含有させることにより、さらに機械的
物性、特にＩＬＳＳ（層間せん断力）、曲げ強度に優れ
た繊維強化複合材料とすることができる。該無機充填材
としては、それが球形の場合は直径が、その他の形状で
は短軸長が、集合している強化長繊維の繊維と繊維の間
の距離より短いものである。ヤーンとして集合している
強化長繊維の繊維と繊維の間隙に該無機充填材を含有し
ている樹脂組成物を存在させることにより、上述の性能
が発現する。In the present invention, by incorporating a specific inorganic filler in the epoxy resin composition, a fiber reinforced composite material having more excellent mechanical properties, particularly ILSS (interlayer shearing force) and bending strength can be obtained. .. The inorganic filler has a diameter when it is spherical, and a minor axis length which is shorter than the distance between the fibers of the reinforced long fibers which are assembled in other shapes. The presence of the resin composition containing the inorganic filler in the interstices between the fibers of the reinforced long fibers gathered as yarns causes the above performance to be exhibited.
【００２３】なお該無機充填材の形状の物性への影響と
しては、針状、薄片状、板状、ウィスカー、棒状及び長
手方向に伸ばされた楕円体等の形状のものが、弾性率の
向上に効果的である。Regarding the influence of the shape of the inorganic filler on the physical properties, the shape of needle-like, flaky, plate-like, whisker, rod-like, and ellipsoids elongated in the longitudinal direction has an improved elastic modulus. Is effective in.
【００２４】本発明で用いる熱硬化性樹脂組成物、例え
ばエポキシ樹脂組成物の硬化後の弾性率は、３ＧＰａ以
上であることが好ましい。３ＧＰａ以上のエポキシ樹脂
組成物を用いることにより、ヤーンプリプレグの硬化後
の補強体の圧縮強度を向上させることができる。The elastic modulus after curing of the thermosetting resin composition used in the present invention, for example, the epoxy resin composition, is preferably 3 GPa or more. By using an epoxy resin composition of 3 GPa or more, it is possible to improve the compressive strength of the reinforcing body after curing the yarn prepreg.
【００２５】本発明において、芳香族ポリアラミド繊維
からなるヤーンに熱硬化性樹脂を含浸させる方法は特に
限定されない。例えば、熱硬化性樹脂組成物を溶媒に分
散、溶解または希釈し熱硬化性樹脂組成物液とし、その
液の中にヤーンを浸漬した後溶媒を乾燥除去する方法が
ある。溶媒中の熱硬化性樹脂組成物は完全に溶解してい
ることを必須としないが、一部またはすべてが溶解しな
い場合は、微粒子として溶媒中に均一に分散させること
が望ましい。In the present invention, the method of impregnating the yarn made of aromatic polyaramid fiber with the thermosetting resin is not particularly limited. For example, there is a method of dispersing, dissolving or diluting a thermosetting resin composition in a solvent to prepare a thermosetting resin composition liquid, immersing the yarn in the liquid, and then removing the solvent by drying. Although it is not essential that the thermosetting resin composition in the solvent is completely dissolved, if a part or all of the thermosetting resin composition is not dissolved, it is desirable that the thermosetting resin composition is uniformly dispersed in the solvent as fine particles.
【００２６】この方法によれば、樹脂組成物をヤーンに
均一に、損傷なく含浸させ得る。また、この熱硬化性樹
脂組成物液による含浸方法は、ヤーンプリプレグ中の樹
脂組成物の含有率を該液中の樹脂組成物の濃度によって
容易に調整が可能である。樹脂の含浸装置としては、例
えばＪＩＳ Ｒ７６０１の図面に記載の装置の一部分を
例示することができる。According to this method, the resin composition can be impregnated into the yarn uniformly and without damage. In addition, in this impregnation method with the thermosetting resin composition liquid, the content of the resin composition in the yarn prepreg can be easily adjusted by the concentration of the resin composition in the liquid. As the resin impregnation device, for example, a part of the device described in the drawing of JIS R7601 can be exemplified.
【００２７】溶媒としては、アセトン、メチルイソブチ
ルケトン、エチレングリコールモノメチルエーテル、ト
ルエン、塩化メチレン、トリクロロエチレン等を例示す
ることができる。Examples of the solvent include acetone, methyl isobutyl ketone, ethylene glycol monomethyl ether, toluene, methylene chloride, trichloroethylene and the like.
【００２８】また熱硬化性樹脂組成物が硬化しない温度
で溶融するものには、溶媒を用いずにその融液にヤーン
を浸漬する方法、溶融した熱硬化性樹脂組成物をヤーン
に塗布した後、圧着したロールの間隙を通して含浸する
方法、さらには熱硬化性樹脂組成物粉末を粉体塗装法に
よりヤーンに塗布し、加熱溶融させ含浸させる方法等用
いられる。For those which melt at a temperature at which the thermosetting resin composition does not cure, a method of immersing the yarn in the melt without using a solvent, after applying the molten thermosetting resin composition to the yarn, Further, a method of impregnating through a gap between pressure-bonded rolls, a method of applying a thermosetting resin composition powder to a yarn by a powder coating method, and heating and melting to impregnate the yarn are used.
【００２９】[0029]
【実施例】以下、実施例により本発明を具体的に説明す
る。実施例及び比較例における試験・評価方法または判
定基準は次に示すとおりである。 （１）ヤーンプリプレグの樹脂含有率 ヤーンプリプレグをテトラヒドロフランで洗って樹脂を
除去し、その減量から算出した。 （２）ヤーンプリプレグのタック（粘着性） ヤーンプリプレグをワインダーに設置された直径８０ｍ
ｍ、長さ２８０ｍｍの紙管ボビンに、トラバースピッチ
７０ｍｍ、張力７５ｇ、速度３ｍ／分で巻き取った。次
いで、巻き取り品をクリールスタンドに設置し３０ｍ／
分の速さで１０ｍ巻き出した。巻き出しに際して、バッ
クテンションが３００ｇ未満でスムーズに巻き出せるも
のを「タック無」、バックテンションが３００〜７００
ｇで巻き出せるものを「タックやや有」とした。 （３）接着性評価 ＡＳＴＭ Ｄ２１３８−７２（以下Ｈテストと呼ぶ）に
準じて測定した。すなわち、本発明のヤーンプリプレグ
または比較例のＰＰＴＡ繊維製コードを未加硫 ゴムシ
ートに積層して所定形状の試験片を作成し、測定に供し
た。ここで用いた未加硫ゴムコンパウンドは、天然ゴム
１００重量部、ステアリン酸４重量部、酸化亜鉛（Ｚｎ
Ｏ）５重量部、ＨＡＦブラック５０重量部、芳香族プロ
セスオイル（共同石油（株）製：商品名ソニックＸ−１
００）３重量部、老化防止剤（住友化学工業（株）製：
商品名アンチゲン３Ｃ）１重量部、加硫促進剤（住友化
学工業（株）製：商品名ソクシノールＣＺ）０．５重量
部及び硫黄０．１重量部を混練してなるものであった。EXAMPLES The present invention will be specifically described below with reference to examples. The test / evaluation methods or criteria in Examples and Comparative Examples are as follows. (1) Resin content of yarn prepreg The resin was removed by washing the yarn prepreg with tetrahydrofuran to calculate the weight loss. (2) Tack (adhesiveness) of the yarn prepreg The diameter of the yarn prepreg installed in the winder is 80 m.
It was wound on a paper tube bobbin having a length of m and a length of 280 mm at a traverse pitch of 70 mm, a tension of 75 g and a speed of 3 m / min. Then, the wound product is placed on the creel stand and 30m /
Unwind 10m at the speed of minute. When unwinding, the one with a back tension of less than 300 g that can be smoothly unwound is "no tack", and the back tension is 300 to 700.
Those that can be unwound with g are "tacky". (3) Adhesiveness Evaluation Measured according to ASTM D2138-72 (hereinafter referred to as H test). That is, the yarn prepreg of the present invention or the PPTA fiber cord of the comparative example was laminated on an unvulcanized rubber sheet to prepare a test piece having a predetermined shape, and the test piece was subjected to measurement. The unvulcanized rubber compound used here was 100 parts by weight of natural rubber, 4 parts by weight of stearic acid, and zinc oxide (Zn oxide).
O) 5 parts by weight, HAF black 50 parts by weight, aromatic process oil (Kyodo Oil Co., Ltd .: trade name Sonic X-1)
00) 3 parts by weight, anti-aging agent (Sumitomo Chemical Co., Ltd .:
1 part by weight of Antigen 3C (trade name), 0.5 part by weight of a vulcanization accelerator (Succinol CZ, trade name, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 part by weight of sulfur were kneaded.
【００３０】実施例１ ビスフェノールＡ型のエポキシ樹脂：スミエポキシＥＬ
Ａ１２８（商品名、住友化学工業（株）製）２９重量
部、同じくスミエポキシＥＳＡ０１１（同）７１重量部
に、硬化剤として２─エチルメチルイミダゾール５重量
部を６０°Ｃに加熱した３本ロールミキサー（（株）井
上製作所製）を用いて均一に混合し、エポキシ樹脂組成
物１Ｋｇを得た。この樹脂組成物の硬化後の曲げ弾性率
は３．２ＧＰａであった。また、６０℃における粘度は
Ｅ型粘度形（（株）東京計器製）による測定で９５０ポ
イズであった。次にこの樹脂組成物を濃度が３０重量％
になるようにトリクロロエチレンに溶解して樹脂組成物
液を調製し、該液を内部に１本のローラーを備えた含浸
槽に入れた。Example 1 Bisphenol A type epoxy resin: Sumiepoxy EL
29 parts by weight of A128 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), 71 parts by weight of Sumiepoxy ESA011 (the same), and 5 parts by weight of 2-ethylmethylimidazole as a curing agent, heated to 60 ° C. (Manufactured by Inoue Seisakusho Co., Ltd.) was uniformly mixed to obtain 1 kg of an epoxy resin composition. The flexural modulus of the resin composition after curing was 3.2 GPa. The viscosity at 60 ° C. was 950 poise as measured by an E-type viscosity type (manufactured by Tokyo Keiki Co., Ltd.). Next, this resin composition was added at a concentration of 30 wt%.
Was dissolved in trichloroethylene to prepare a resin composition liquid, and the liquid was placed in an impregnation tank equipped with one roller inside.
【００３１】長さ１０００ｍのポリパラフェニレンテレ
フタルアミド繊維ヤーン（アクゾ社製：商品名トワロン
１０００、繊度８４０ｄｔｅｘ）をリング式の精紡機を
用いて１０回／ｍの撚りを付与し、このストランドを含
浸槽内をローラーに沿わせて通過させることにより、樹
脂組成物溶液を含浸させ、次いで長さ２ｍ、内部温度１
５０℃の乾燥炉を通して溶媒を揮散させた後、紙管に巻
き取り本発明のヤーンプリプレグを得た。このヤーンプ
リプレグの接着性等を測定して下記の表１に示した。こ
のヤーンプリプレグは室温で柔軟性があり、容易に折り
返すことができた。Polyparaphenylene terephthalamide fiber yarn having a length of 1000 m (manufactured by Akzo: trade name Twaron 1000, fineness 840 dtex) was twisted 10 times / m using a ring type spinning machine, and this strand was impregnated. The resin composition solution is impregnated by passing through the inside of the tank along the rollers, and then the length is 2 m and the internal temperature is 1
After the solvent was volatilized through a drying oven at 50 ° C., it was wound on a paper tube to obtain a yarn prepreg of the present invention. The adhesiveness of this yarn prepreg was measured and shown in Table 1 below. This yarn prepreg was flexible at room temperature and could be easily folded.
【００３２】実施例２ ビスフェノールＡ型のエポキシ樹脂：スミエポキシＥＬ
Ａ１３４（商品名、住友化学工業（株）製）７０重量
部、クレゾールノボラック型のエポキシ樹脂：スミエポ
キシＥＳＣＮ２２０（同）３０重量部に、硬化剤として
ジシアンジアミド６重量部、硬化促進剤としてジクロロ
フェニル−１，１−ジメチルウレア４重量部を実施例１
と同じ方法で配合し、エポキシ樹脂組成物１ｋｇを得
た。この樹脂組成物の硬化後の曲げ弾性率は３．９ＧＰ
ａ、１６０℃における粘度は１３００ポイズであった。
この樹脂組成物を使用して実施例１と同じ方法でヤーン
プリプレグを得た。評価結果は第１表で示した。このヤ
ーンプリプレグは室温で柔軟性があり容易に折返すこと
ができた。Example 2 Bisphenol A type epoxy resin: Sumiepoxy EL
70 parts by weight of A134 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), 30 parts by weight of cresol novolac type epoxy resin: Sumiepoxy ESCN220 (same), 6 parts by weight of dicyandiamide as a curing agent, and dichlorophenyl-1, as a curing accelerator. 4 parts by weight of 1-dimethylurea was used in Example 1
Compounding was carried out in the same manner as above to obtain 1 kg of an epoxy resin composition. The flexural modulus of this resin composition after curing is 3.9 GP.
a, the viscosity at 160 ° C. was 1300 poise.
Using this resin composition, a yarn prepreg was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. This yarn prepreg was flexible at room temperature and could be easily folded.
【００３３】実施例３ ４，４’−ジアミノジフェニルメタンポリグリシジルエ
ーテルであるスミエポキシＥＬＭ−４３４（商品名、住
友化学工業（株）製）９０重量部、前記スミエポキシＥ
ＳＣＮ２２０を１０重量部に、硬化剤として４，４’−
ジアミノジフェニルスルフォンを３８重量部、硬化促進
剤として三フッ化ホウ素−ピペリジン錯体１．５重量部
を実施例１と同じ方法で配合し、エポキシ樹脂組成物を
得た。この樹脂組成物の硬化後の曲げ弾性率は４．２Ｇ
Ｐａ、６０℃における粘度は１６００ポイズであった。
この樹脂組成物を使用して実施例１と同じ方法でヤーン
プリプレグを得た。その評価結果を第１表に示した。こ
のヤーンプリプレグは室温で柔軟性があり容易に折返す
ことができた。Example 3 90 parts by weight of Sumiepoxy ELM-434 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is 4,4'-diaminodiphenylmethane polyglycidyl ether, the above Sumiepoxy E
10 parts by weight of SCN220 and 4,4'- as a curing agent
38 parts by weight of diaminodiphenyl sulfone and 1.5 parts by weight of boron trifluoride-piperidine complex as a curing accelerator were blended in the same manner as in Example 1 to obtain an epoxy resin composition. The flexural modulus of this resin composition after curing is 4.2 G.
The viscosity at Pa of 60 ° C. was 1600 poise.
Using this resin composition, a yarn prepreg was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. This yarn prepreg was flexible at room temperature and could be easily folded.
【００３４】実施例４ 実施例１〜３のヤーンプリプレグと未加硫ゴムシートを
積層してタイヤ用のプライを製造する。本発明のヤーン
プリプレグは、タイヤ製造工程における加熱時にゴム加
硫と同時に熱硬化され、加硫ゴムとの接着性に優れた補
強体を形成する。Example 4 A ply for a tire is manufactured by laminating the yarn prepregs of Examples 1 to 3 and an unvulcanized rubber sheet. The yarn prepreg of the present invention is heat-cured at the same time as rubber vulcanization during heating in the tire manufacturing process to form a reinforcement having excellent adhesiveness to vulcanized rubber.
【００３５】比較例１ 実施例１で用いたトワロン１０００（８４０ｄｔｅｘ）
を、前記スミエポキシＥＬＡ−１２８を１００重量部、
酸無水物ＨＮ５５００（商品名、日立化成工業（株）
製）９０重量部及びトリ−２，４，６ジメチルアミノメ
チルフェノール（商品名：ＤＭＰ−３０、日本化薬
（株）製）１重量部からなるエポキシ樹脂組成物（２３
℃での粘度が６５０センチポイズ）に含浸し、１２０℃
４時間の硬化処理を行いＰＰＴＡタイヤコードを得た。
樹脂含有量は３２重量％であった。得られたＰＰＴＡタ
イヤコードは柔軟性を欠き、手で曲げると容易に折れ
た。接着性試験の結果を第１表に示した。Comparative Example 1 Twaron 1000 (840 dtex) used in Example 1
100 parts by weight of the Sumiepoxy ELA-128,
Acid anhydride HN5500 (trade name, Hitachi Chemical Co., Ltd.)
Manufactured by K.K.) 90 parts by weight and 1 part by weight of tri-2,4,6 dimethylaminomethylphenol (trade name: DMP-30, manufactured by Nippon Kayaku Co., Ltd.) (23)
Impregnated with a viscosity of 650 centipoise at ℃, 120 ℃
After curing for 4 hours, a PPTA tire cord was obtained.
The resin content was 32% by weight. The obtained PPTA tire cord lacked flexibility and easily bent when bent by hand. The results of the adhesion test are shown in Table 1.
【００３６】比較例２ 比較例１と同様にして、エポキシ樹脂組成物を含浸した
未硬化のＰＰＴＡタイヤコードを、下記のＲＦＬ液に浸
漬し、ついで１５０℃及び２４０℃のオーブン中に、そ
れぞれ２分間通過させて乾燥及び硬化させた。ここで用
いたＲＦＬ液は、レゾルシン−ホルマリン樹脂として該
樹脂のプレ縮合物（住友化学工業（株）製、商品名：ス
ミカノール７００、７５重量％水溶液）４．６重量部、
ゴムラテックスとしてビニルピリジン−スチレン−ブタ
ジエンゴムラテックス（住友ノーガタック（株）製、商
品名：ピラテックス、４１重量％水溶液）５０．０重量
部、ホルムアルデヒド（３７重量％水溶液）２．３重量
部、２５重量％アンモニア水１．３重量部及び純水４
１．８重量部からなるものであり、レゾルシン−ホルマ
リン樹脂／ゴムラテックス固形分重量比１６．８／１０
０、全固形分濃度２５重量％のものであった。ＲＦＬ液
処理後硬化して得られたＰＰＴＡコードは柔軟性を欠
き、手で曲げると容易に折れた。接着性試験の結果を第
１表に示した。Comparative Example 2 In the same manner as in Comparative Example 1, an uncured PPTA tire cord impregnated with an epoxy resin composition was dipped in the RFL solution described below and then placed in an oven at 150 ° C. and 240 ° C. for 2 times, respectively. It was passed for a minute to dry and cure. The RFL solution used here was 4.6 parts by weight of a precondensate of the resin as a resorcin-formalin resin (Sumitomo Chemical Co., Ltd., trade name: Sumikanol 700, 75% by weight aqueous solution).
As a rubber latex, vinyl pyridine-styrene-butadiene rubber latex (Sumitomo Nogatac Co., Ltd., trade name: Pylatex, 41% by weight aqueous solution) 50.0 parts by weight, formaldehyde (37% by weight aqueous solution) 2.3 parts by weight, 1.3 parts by weight of 25% by weight aqueous ammonia and pure water 4
It is composed of 1.8 parts by weight, and the resorcin-formalin resin / rubber latex solid content weight ratio is 16.8 / 10.
0, the total solid content was 25% by weight. The PPTA cord obtained by curing after treatment with the RFL liquid lacked flexibility and was easily broken when bent by hand. The results of the adhesion test are shown in Table 1.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】本発明の芳香族ポリアミド繊維からなる
ヤーンプリプレグは、柔軟性が良好で加工性と操作性に
優れる。マトリックスである熱硬化性樹脂組成物は室温
で半固形であり、ヤーンプリプレグは自由な形状に加工
できる。特に折返しもできるので、カーカス用補強材と
しても、フォールデットベルト用としても容易に加工さ
れる。また、必要に応じて熱硬化時にプリテンションを
かけて成形することも可能である。プリテンションをか
けて成形した場合には、芳香族ポリアラミド繊維の欠点
である圧縮強度の弱さが緩和される。また、ゴムとの複
合において従来の繊維コードに必須であったＲＦＬ液に
よる処理をしなくてもゴムとの接着性が良好であり、Ｒ
ＦＬ処理工程の省略による製造工程の簡素化は工業的に
有用である。The yarn prepreg made of the aromatic polyamide fiber of the present invention has good flexibility and excellent workability and operability. The thermosetting resin composition that is the matrix is semi-solid at room temperature, and the yarn prepreg can be processed into any desired shape. In particular, since it can be folded back, it can be easily processed as a reinforcing material for carcass or for folded belt. Further, it is also possible to apply pre-tension at the time of thermosetting as necessary for molding. When pretensioning is applied, the weakness of the compressive strength, which is a drawback of the aromatic polyaramid fiber, is alleviated. Further, in the case of compounding with rubber, the adhesiveness with rubber is good without the treatment with the RFL liquid, which is essential for the conventional fiber cord, and R
Simplification of the manufacturing process by omitting the FL treatment process is industrially useful.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ６０Ｃ 9/18 8408−3Ｄ // Ｂ２９Ｋ 21:00 77:00 105:12 Ｂ２９Ｌ 30:00 4Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B60C 9/18 8408-3D // B29K 21:00 77:00 105: 12 B29L 30:00 4F
Claims (2)
０〜８０重量％に熱硬化性樹脂２０〜５０重量％を含浸
してなることを特徴とする未加硫ゴムシート積層用のヤ
ーンプリプレグ。1. A yarn 5 comprising an aromatic polyaramid fiber.
A yarn prepreg for laminating an unvulcanized rubber sheet, which is obtained by impregnating 0 to 80% by weight with a thermosetting resin of 20 to 50% by weight.
ゴムシートに積層して加熱する工程を含むことを特徴と
するタイヤの製造方法。2. A method of manufacturing a tire, comprising a step of laminating the yarn prepreg according to claim 1 on an unvulcanized rubber sheet and heating the laminated sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4034821A JPH05229033A (en) | 1992-02-21 | 1992-02-21 | Yarn prepreg and production of tire using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4034821A JPH05229033A (en) | 1992-02-21 | 1992-02-21 | Yarn prepreg and production of tire using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05229033A true JPH05229033A (en) | 1993-09-07 |
Family
ID=12424866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4034821A Pending JPH05229033A (en) | 1992-02-21 | 1992-02-21 | Yarn prepreg and production of tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05229033A (en) |
-
1992
- 1992-02-21 JP JP4034821A patent/JPH05229033A/en active Pending
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