JPH024715B2 - - Google Patents
Info
- Publication number
- JPH024715B2 JPH024715B2 JP61269797A JP26979786A JPH024715B2 JP H024715 B2 JPH024715 B2 JP H024715B2 JP 61269797 A JP61269797 A JP 61269797A JP 26979786 A JP26979786 A JP 26979786A JP H024715 B2 JPH024715 B2 JP H024715B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- liquid
- reinforcing fibers
- latex
- weight
- 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.)
- Expired - Lifetime
Links
- 239000007788 liquid Substances 0.000 claims description 56
- 229920001971 elastomer Polymers 0.000 claims description 47
- 239000005060 rubber Substances 0.000 claims description 47
- 239000012783 reinforcing fiber Substances 0.000 claims description 35
- 229920000126 latex Polymers 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000004816 latex Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 229920001897 terpolymer Polymers 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 150000002611 lead compounds Chemical class 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 claims description 5
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000003365 glass fiber Substances 0.000 description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002681 hypalon Polymers 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- MKZXROSCOHNKDX-UHFFFAOYSA-N 1,4-dinitrosobenzene Chemical compound O=NC1=CC=C(N=O)C=C1 MKZXROSCOHNKDX-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
［発明の目的］
（産業上の利用分野）
本発明はゴムベルト、タイヤ等のゴル製品の補
強用に用いるゴム補強用繊維の処理方法に関する
ものである。
（従来の技術）
ゴムベルト、タイヤ等のゴム製品の強度を増大
させる為、ガラス繊維ヤーン等の補強繊維が広く
用いられる。
ゴムベルト等のゴム製品は繰返し屈曲応力を受
けるため屈曲疲労を生じて性能が低下し、補強剤
とゴムマトリツクスの間に剥離が生じ易い。
このような剥離或は性能の劣化を防止し、充分
な補強効果を得るためには、補強繊維とゴムとの
馴染み、接着力を大きくする必要があり、このた
め補強繊維表面に処理剤が塗布される。
処理剤としては各種組成のものが提案されてい
る。
例えばビニルピリジン−スチレン−ブタジエン
のターポリマーラツクス及びレゾルシンとホルマ
リンの水溶性縮合物を併用した処理剤、或はゴム
ラテツクスを添加した処理剤等各種処理剤が提案
されている。（特開昭55−114551号参照）
又ポリイソシアネート、ポリニトロソ芳香族化
合物、酸性のハロゲン含有ポリマーを含む処理液
も提案されている。（特開昭49−14546号参照）
しかしながらこれらの処理液を使用した処理法
は
(1) 充分な接着力が得られない。
(2) 充分な屈曲強度を有するゴム製品が得難い。
等の欠点を有していた。
近時、自動用のエンジン附近の温度上昇に伴な
い、タイミングベルト用のゴムとしてクロロプレ
ンゴム、クロロスルフオニル化ポリエチレン、水
素化ニトリルゴムのような耐熱性のゴムが使用さ
れるようになつて来たが、このような耐熱性のゴ
ムは接着性が一般のゴムに比して小さいため上述
の欠点は一般のゴムに比し大きくなり易く、工業
的に満足すべきゴム補強用繊維の処理方法は知ら
れていなかつた。
（発明が解決しようとする問題点）
本発明は従来技術の有していた前述の欠点を解
消することを目的とするものである。
［発明の構成］
（問題点を解決するための手段）
本発明は前述の問題点を解決すべくなされたも
のであり、ビニールピリジン−スチレン−ブタジ
エンのターポリマーラテツクス、ゴムラテツクス
及びレゾルシン−ホルムアルデヒドの水溶性縮合
物を含む第１液で処理した後、ハロゲン含有ポリ
マー、イソシアネートを含む第２液で処理するこ
とを特徴とするゴム補強用繊維の処理方法、ビニ
ールピリジン−スチレン−ブタジエンのターポリ
マーラテツクス、ゴムラテツクス及びレゾルジン
−ホルムアルデヒドの水溶性縮合物を含む第１液
で処理した後、ハロゲン含有ポリマー、イソシア
ネート及び加硫剤を含む第２液で処理することを
特徴とするゴム補強用繊維の処理方法並びにビニ
ールピリジン−スチレン−ブタジエンのターポリ
マーラテツクス、ゴムラテツクス、及びレゾルジ
ン−ホルムアルデヒドの水溶性縮合物を含む第１
液で処理した後、ハロゲン含有ポリマー、イソシ
アネート、加硫剤及び鉛化合物を含む第２液で処
理することを特徴とするゴム補強用繊維の処理方
法を提供するものである。
次に、特許請求の範囲第１項記載の発明（第１
発明）を更に具体的に説明する。
先ず第１液に就いて説明する。
ビニルピリジン−スチレン−ブタジエンのター
ポリマーラテツクス（以下ターポリマーラテツク
スと呼ぶ）としては、ビニルピリジン、スチレ
ン、ブタジエンの重量割合が10〜20：10〜20：60
〜80のものが特に適当であり、Pyratex（商品名、
住友ノーガタツク社製）、0650（商品名、日本合成
ゴム製）、Nipol 2518FS（商品名、日本ゼオン製）
等が好適に使用できる。
ゴムラテツクスとしては、ゴム補強繊維用処理
剤として使用される比較的低重度のラテツクス、
特にブタジエンゴムラツテクスが適当である。
0700（商品名、日本合成ゴム製）、Niipl LX111
（商品名、日本ゼオン製）等が好適に使用できる。
レゾルシン−ホルマリンの水溶性縮合物（以下
単に縮合物という）としては、レゾルシンとホル
ムアルデヒドを水酸化アルカリ、アンモニア、ア
ミンなどのアルカリ性触媒の存在下で反応させて
得られるレゾルシンとホルムアルデヒドのオキシ
メチル基に富んだ水溶性の初期の付加縮合物（レ
ゾール）が好適に使用できる。特にレゾルシンと
フオルムアルデヒドをモル比で１：0.3〜2.5の割
合で反応させたものが好ましい。
第１液においてはターポリマーラテツクスとラ
テツクスの合計量（総ラテツクスと呼ぶ）に対す
るラテツクスの割合を2.5〜50wt％、総ラテツク
スに対する縮合物の割合を2.5〜25wt％の間とな
るよう三成分を常法に従い均一に混合する。なお
上記比率はいずれも固形分としての比率である。
総ラテツクスに対するラテツクスの割合があま
り大きいと、本発明処理剤で処理された補強繊維
の粘着性が過大となり、撚糸工程でトラブルが発
生し易く、又耐熱性が低下する。
上記割合があまり小さいと繰返し応力を受けた
場合の剥離防止効果が不充分となり、特に高温多
湿還境で使用した場合の剥離が生じ易くなる。
総ラテツクスに対する縮合物の割合があまり大
きいと本発明処理剤で処理した補強繊維が固くな
り、屈曲疲労が生じ易くなる。
又この場合があまり小さいと、ゴムマトリツク
スとの接着力が低下し易い。
上述した混合物第１液の濃度即ち処理剤中のタ
ーポリマーラテツクス、ラテツクス、縮合物の合
計量の重量％は10〜50％好ましくは20〜40％とす
るのが適当である。
濃度があまり小さいと補強繊維への附着が不充
分となり、又濃度があまり大きいと安定性が悪く
なり、ゲル化し易くなる。
第１液は上述したターポリマーラテツクス、ラ
テツクス、縮合物を必須成分とするものであるが
必要に応じ、ラテツクスの安定剤、老化防止剤等
を添加することもできる。
次に第２液について説明する。
イソシアネートとしては、メチレンジ−（フエ
ニルイソシアネート）（MDI）又はトルエンジイ
ソシアネート（TDI）、トリフエニルメタントリ
イソシアネート、ナフタリンジイソシアネート等
が好適に使用できる。イソシアネート単量体は揮
発性が大きいため２量体等の比較的分子量が小さ
く、反応性に富んだポリイソシアネートが好適に
使用できる。好ましい重合度２〜10である。
ハロゲン含有ポリマーとしては塩素化ゴム、ク
ロロプレン、塩素化ポリエチレン、塩素化エチレ
ン−プロピレン共重合体、塩素化ポリ塩化ビニ
ル、クロロスルフオニル化ポリエチレン等が使用
できるがクロロスルフオニル化ポリエチレンが特
に好適な結果を与える。
イソシアネートとハロゲン含有ポリマーの割合
は10〜100：100とするのが適当であり、イソシア
ネートの割合があまり大きいと屈曲疲労性並びに
耐熱性が悪化する。又イソシアネートの割合があ
まり小さいと接着性が低下する。
第２液の濃度（イソシアネートとハロゲン含有
ポリマーの合計量の重量％）は３〜15wt％好ま
しくは５〜10wt％とするのが適当であり、この
濃度があまり大きいと液の粘度が大となり、ムラ
が出来易くなり、又この濃度があまり小さいと附
着量が減少し、充分な効果が得られなくなる。
次に、特許請求の範囲第２項記載の発明（第２
発明）に就いて更に具体的に説明する。
第２発明においては、第１発明の第２液に代
え、ハロゲン含有ポリマー、イソシアネート及び
加硫剤を含む第２液を用いてゴム補強用繊維を処
理することにより接着性を向上させる。
第２発明のその他の構成要件は第１発明と同様
なので、以下加硫剤に就いてのみ説明する。
加硫剤としてはポリニトロソ芳香族化合物（例
えばｐ−ジニトロソベンゼン）、テトラクロロベ
ンゾキノン、ポリｐ−ジニトロソベンゼン、ｐ，
p′−ジベンゾイル、ベンゾキノンジオキシム、ｐ
−ベンゾキノンジオキシムが例示されるが、テト
ラクロロベンゾキノン、ポリｐ−ジニトロソベン
ゼン、ｐ，p′−ジベンゾイルベンゾキノンジオキ
シム、ｐ−ベンゾキノンジオキシムが特に好まし
い。
第２液中の加硫剤の量は0.3〜2wt％、望ましく
は0.6〜1wt％程度とするのが適当であり、この量
があまり少ないと効果が充分でなく、第１液層と
第２液層との間の剥離が生じ易くなる。
又この量があまり多いとゴムマトリツクと第２
液層との剥離が生じ易くなる。
次に、特許請求の範囲第３項記載の発明（第３
発明）に就いて更に具体的に説明する。
第３発明においては、第２発明の第２液に代
え、ハロゲン含有ポリマー、イソシアネート及び
加硫剤を含む第２液を用いてゴム補強用繊維を処
理することにより耐水性を向上させる。
第３発明のその他の構成要件は第２発明と同様
なので、以下鉛化合物に就いてのみ説明する。
鉛化合物としては、リサージ、マレイン酸鉛、
フタル酸鉛が特に好ましい。
第２液中の鉛化合物の量は0.5〜5wt％、好まし
くは１〜3wt％とするのが適当である。
上述した第１発明、第２発明、第３発明（以下
本発明と総称する）の方法によつて処理すべき補
強繊維に特に限定はないが、ガラス繊維を用いる
のが実際的である。例えば、太さ9μのガラス繊
維に集束剤を附与して200本程度集束したガラス
繊維が好適に使用できる。
このような補強繊維を３本引揃え、これにに第
１液を12〜22wt％望ましくは16〜20wt％常法に
従い塗布する。
第１液を附与後好ましくは充分乾繰させた後、
第２液を常法に従い塗布する。第１液の乾繰は
200〜350℃で行うのが望ましい。
第２液の塗布量は補強繊維に対し0.5〜5wt％、
望ましくは２〜4wt％とするのが適当である。第
２液を塗布した後好ましくは120〜200℃において
乾操する。
なお、上述の第１液を塗布した補強繊維に2.54
cm（１イシチ）当り0.5〜4.0程度のＳ、又はＺ撚
り（下撚り）を与えたものを更に２〜13本程度引
揃えて2.54cm当り0.5〜3.0程度の、下撚りと逆方
向の撚り（上撚り）を与えてヤーンとし、これに
第２液を塗布するのが望ましい。
本発明処理剤を附与した補強繊維で補強すべき
ゴムの種類に特に限定はないが、ハイパロン、ニ
トリルゴム、水素添加ニトリルゴム等が例示で
き、極めて好適な結果をうることができ、耐熱
性、耐久性の良好なタイミングベルト等の補強ゴ
ム製品が得られる。
（作 用）
本発明第１液は補強繊維に対する馴染みが良好
であり、補強繊維に強固に接着された第１層が形
成される。
第２液は補強繊維との接着性は不充分であるが
第１液と反応性を有し、第２液により形成された
第２層は第１層と一体化され、第２層は第１層を
介して補強繊維に強固に接着される。そして第２
層はゴムマトリツクスと相溶性を有し、ゴムマト
リツクスと強固に結合し、好適な結果が得られる
ものと思われる。
又第２発明においては第２液中に加硫剤を添加
することにより接着性を向上させ、更に第３発明
においては第２液中に鉛化合物を添加することに
より耐水性をも向上させる。
実施例 １
ビニルピリジン、スチレン及びブタジエンを
15：15：70の割合で含有するビニルピリジン−ス
チレン−ブタジエンのターポリマーラテツクス
（Pyratex、商品名、住友ノーガタツク社製、タ
ーポリマーの含有量41wt％）、65重量部、ブタジ
エンラテツクス（0700、商品名、日本合成ゴム
製、ブタジエンの含有量57wt％）、８重量部、レ
ゾルシンとホルムアルデヒドの附加縮合物（レゾ
ール）を20wt％含む水溶液を15重量部、水12重
量部の混合物に、更に老化防止剤として鉱油の乳
化物（鉱油の含有量55wt％）１重量部、アンモ
ニア水（濃度18wt％）を１重量部加えて第１液
を得た。
クロロスルフオニル化ポリエチレン（ハイパロ
ン40、商品名、昭和ネオプレン社製）10部、ポリ
イソシアネート（MR−200、商品名、日本ポリ
ウレタン社製）５部、ドルエンを加えて、濃度
10wt％の第２液を得た。
第１液を、9μのガラス繊維を200本集束してな
るガラス繊維束３本を引揃え常法に従つて附与し
た。（固型分17wt％）。250℃で１分間乾繰後、こ
のガラス繊維束を2.54cm当り4.0回のＺ撚り（下
撚り）を与え、更にこの下撚りを与えた繊維束を
13本引揃えて2.54cm当り2.1回のＳ撚り（上撚り）
を施したものに第２液を附与した。（固型分３％）
これを130℃で１分間乾繰したものを、補強繊維
として使用し試験片を作成した。
ゴムの種類
水素添加ニトリルゴム100重量部に対しカーボ
ンブラツク40重量部、亜鉛華５重量部、ステアリ
ン酸１重量部、老化防止剤２重量部、加硫促進剤
３重量部、可塑剤５重量部を配合したもの。
試験片１
厚み１mm、幅５mm、長さ300mmのゴムシートの
間に上記補強繊維を２本挟んでプレスし、150℃
で、20分間加硫
試験片２
厚み３mm、幅25.4mm、長さ100mmのゴムシート
の間に上記補強繊維を隙間なく並べ、ブレスし
て、150℃で、20分間加硫
この試験片の引張り強度並びにこの試験片１を
120℃のオーブン中に24時間放置後MIT試験機を
使用し、屈曲応力を3000回与えた後の試験片１の
引張り強度を測定した。
この試験片２並びに100℃の熱水中に１時間放
置した後の試験片を、オートグラフを用い、50
mm／minの引帳り速度で剥離し、接着力を測定し
た。
上記テスト結果を別表に示す。
実施例 ２
実施例１のゴムに代え、ハイパロン100重量部
に対し、カーボナブラツク50重量部、MgO10重
量部、可塑剤10重量部、老化防止剤１重量部、加
硫促進剤２重量部を配合したものを使用し、実施
例１と同様なテストを行つた結果を別表に示す。
実施例 ３
ビニルピリジン、スチレン及びブタジエンを
15：15：70の割合で含有するビニルピリジン−ス
チレン−ブタジエンのターポリマーラテツクス
（Pyratex、商品名、住友ノーガタツク社製、タ
ーポリマーの含有量41wt％）、65重量部、ブタジ
エンラテツクス（0700、商品名、日本合成ゴム
製、ブタジエンの含有量57wt％）、８重量部、レ
ゾルシンとホルムアルデヒドの附加縮合物（レゾ
ール）を20wt％含む水溶液を15重量部、水12重
量部の混合物に、更に老化防止剤として鉱油の乳
化物（鉱油の含有量55wt％）１重量部、アンモ
ニア水（濃度18wt％）を１重量部加えて第１液
を得た。
クロロスルフオニル化ポリエチレン（ハイパロ
ン40、商品名、昭和ネオプレン社製）10部、ポリ
イソシアネート（MR−200、商品名、日本ポリ
ウレタン社製）５部、ｐ，p′−ジベンゾイルベン
ゾキノンジオキシム２部、ドルエンを加えて、濃
度10wt％の第２液を得た。
第１液を、9μのガラス繊維を200本集束してな
るガラス繊維束３本を引揃え常法に従つて附与し
た。（固型分17wt％）。250℃で１分間乾操後、こ
のガラス繊維束を2.54cm当り4.0回のＺ撚り（下
撚り）を与え、更にこの下撚りを与えた繊維束を
13本引揃えて2.54cm当り2.1回のＳ撚り（上撚り）
を施こしたものに第２液を附与した。（固型物３
％）これを130℃で１分間乾繰したものを、補強
繊維として使用し試験片を作成した。
ゴムの種類
水素添加ニトリルゴム100重量部に対しカーボ
ンブラツク40重量部、亜鉛華５重量部、ステアリ
ン酸１重量部、老化防止剤２重量部、加硫促進剤
３重量部、可塑剤５重量部を配合したもの。
試験片１
厚み１mm、幅５mm、長さ300mmのゴムシートの
間に上記補強繊維を２本挟んでプレスし、150℃
で、20分間加硫
試験片２
厚み３mm、幅25.4mm、長さ100mmのゴムシート
の間に上記補強繊維を隙間なく並べ、プレスし
て、150℃で、20分間加流
この試験片の引張り強度並びにこの試験片１を
120℃のオーブン中に24時間放置後MIT試験機を
使用し、屈曲応力を3000回与えた後の試験片１の
引張り強度を測定した。
この試験片２並びに100℃の熱水中に１時間放
置した後の試験片を、オートグラフ用い、50mm／
minの引張り速度で剥離し、接着力を測定した。
上記テスト結果を別表に示す。
実施例 ４
実施例３のゴムに代え、ハイパロン100重量部
に対し、カーボンブラツク50重量部、MgO10重
量部、可塑剤10重量部、老化防止剤１重量部、加
硫促進剤２重量部を配合したものを使用し、実施
例１と同様なテストを行つた結果を別表に示す。
実施例 ５、６
実施例３、４の第２液のｐ−p′ジベンゾイルベ
ンゾキノンジオキシムに代えテトラクロロベンゾ
キノンを使用し、更にリサージを2wt％加えた第
２液を使用し、実施例１と同様なテストを行つ
た。結果を別表に示す。
比較例 １、２
実施例１と同じ第１液を20wt％塗布した補強
繊維を用いて、以下実施例１、２と同様な試験片
を作成し、同一のテストを行つた。結果を別表に
示す。
比較例 ３、４
比較例１、２の第１液に代え、実施例１と同じ
第２液を用い、実施例１、２と同様な試験片を作
成し、同一のテストを行つた。結果を別表に示
す。
比較例 ５、６
比較例１、２の第１液に代え、実施例３と同じ
第２液を用い、実施例１、２と同様な試験片を作
成し、同一のテストを行つた。結果を別表に示
す。
比較例 ７、８
比較例１、２の第１液に代え、実施例５と同じ
第２液を用い、実施例１、２と同様な試験片を作
成し、同一のテストを行つた。結果を別表に示
す。
[Object of the Invention] (Industrial Application Field) The present invention relates to a method for processing rubber reinforcing fibers used for reinforcing rubber products such as rubber belts and tires. (Prior Art) Reinforcing fibers such as glass fiber yarn are widely used to increase the strength of rubber products such as rubber belts and tires. Rubber products such as rubber belts are subjected to repeated bending stress, which causes bending fatigue, resulting in decreased performance, and peeling between the reinforcing agent and the rubber matrix is likely to occur. In order to prevent such peeling or performance deterioration and obtain a sufficient reinforcing effect, it is necessary to increase the compatibility and adhesive strength between the reinforcing fibers and the rubber. be done. Various compositions of processing agents have been proposed. For example, various processing agents have been proposed, such as a processing agent using a combination of a vinylpyridine-styrene-butadiene terpolymer lattice and a water-soluble condensate of resorcinol and formalin, or a processing agent containing rubber latex. (See JP-A No. 55-114551.) Treatment liquids containing polyisocyanates, polynitroso aromatic compounds, and acidic halogen-containing polymers have also been proposed. (Refer to JP-A No. 49-14546.) However, the processing methods using these processing solutions (1) do not provide sufficient adhesive strength; (2) It is difficult to obtain rubber products with sufficient bending strength. It had the following drawbacks. Recently, with the rise in temperature near automatic engines, heat-resistant rubbers such as chloroprene rubber, chlorosulfonylated polyethylene, and hydrogenated nitrile rubber have come to be used as rubber for timing belts. However, since the adhesion of such heat-resistant rubber is lower than that of ordinary rubber, the above-mentioned drawbacks tend to be greater than that of ordinary rubber. The method was unknown. (Problems to be Solved by the Invention) The present invention aims to solve the above-mentioned drawbacks of the prior art. [Structure of the Invention] (Means for Solving the Problems) The present invention has been made to solve the above-mentioned problems. A method for treating rubber reinforcing fibers, which comprises treating with a first liquid containing a water-soluble condensate and then a second liquid containing a halogen-containing polymer and an isocyanate, a vinyl pyridine-styrene-butadiene terpolymer latte. A treatment for rubber reinforcing fibers, characterized in that the treatment is performed with a first liquid containing a water-soluble condensate of tux, rubber latex, and resordin-formaldehyde, and then treated with a second liquid containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent. A first method comprising a terpolymer latex of vinylpyridine-styrene-butadiene, a rubber latex, and a water-soluble condensate of resorzine-formaldehyde.
The present invention provides a method for treating rubber reinforcing fibers, which comprises treating with a second liquid containing a halogen-containing polymer, an isocyanate, a vulcanizing agent, and a lead compound. Next, the invention described in claim 1 (the first
invention) will be explained in more detail. First, the first liquid will be explained. The vinylpyridine-styrene-butadiene terpolymer latex (hereinafter referred to as terpolymer latex) has a weight ratio of vinylpyridine, styrene, and butadiene of 10 to 20:10 to 20:60.
~80 is particularly suitable, Pyratex (trade name,
(manufactured by Sumitomo Nogatatsu), 0650 (product name, manufactured by Nippon Synthetic Rubber), Nipol 2518FS (product name, manufactured by Nippon Zeon)
etc. can be suitably used. Rubber latex includes relatively low-heavy latex used as a treatment agent for rubber reinforcing fibers,
Particularly suitable is butadiene rubber latex.
0700 (product name, made by Japan Synthetic Rubber), Niipl LX111
(trade name, manufactured by Nippon Zeon), etc. can be suitably used. A water-soluble condensate of resorcin-formalin (hereinafter simply referred to as a condensate) is produced by reacting resorcin and formaldehyde in the presence of an alkaline catalyst such as an alkali hydroxide, ammonia, or an amine. Highly water-soluble initial addition condensates (resols) can be preferably used. Particularly preferred is one in which resorcinol and formaldehyde are reacted at a molar ratio of 1:0.3 to 2.5. In the first liquid, the three components are mixed so that the ratio of latex to the total amount of terpolymer latex and latex (referred to as total latex) is between 2.5 and 50 wt%, and the ratio of condensate to the total latex is between 2.5 and 25 wt%. Mix uniformly according to the usual method. Note that all of the above ratios are based on solid content. If the ratio of latex to total latex is too large, the reinforcing fibers treated with the treatment agent of the present invention will have excessive tackiness, which will likely cause trouble in the yarn twisting process, and will also reduce heat resistance. If the above ratio is too small, the effect of preventing peeling when subjected to repeated stress will be insufficient, and peeling will easily occur especially when used in a high temperature and humid environment. If the ratio of the condensate to the total latex is too large, the reinforcing fibers treated with the treatment agent of the present invention will become hard and prone to bending fatigue. Furthermore, if this value is too small, the adhesive strength with the rubber matrix tends to decrease. The concentration of the first liquid mixture mentioned above, ie, the weight percent of the total amount of terpolymer latex, latex, and condensate in the processing agent, is suitably 10 to 50%, preferably 20 to 40%. If the concentration is too low, adhesion to reinforcing fibers will be insufficient, and if the concentration is too high, stability will deteriorate and gelation will occur easily. The first liquid contains the above-mentioned terpolymer latex, latex, and condensate as essential components, but if necessary, a latex stabilizer, anti-aging agent, etc. may be added. Next, the second liquid will be explained. As the isocyanate, methylene di-(phenyl isocyanate) (MDI), toluene diisocyanate (TDI), triphenylmethane triisocyanate, naphthalene diisocyanate, etc. can be suitably used. Since the isocyanate monomer has high volatility, polyisocyanate such as a dimer having a relatively small molecular weight and high reactivity can be suitably used. The preferred degree of polymerization is 2-10. As the halogen-containing polymer, chlorinated rubber, chloroprene, chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated polyvinyl chloride, chlorosulfonylated polyethylene, etc. can be used, but chlorosulfonylated polyethylene is particularly preferred. gives a good result. It is appropriate that the ratio of isocyanate to halogen-containing polymer be 10 to 100:100; if the ratio of isocyanate is too large, flexural fatigue resistance and heat resistance will deteriorate. Furthermore, if the proportion of isocyanate is too small, the adhesiveness will decrease. It is appropriate that the concentration of the second liquid (weight% of the total amount of isocyanate and halogen-containing polymer) is 3 to 15 wt%, preferably 5 to 10 wt%; if this concentration is too large, the viscosity of the liquid will increase; Unevenness tends to occur, and if this concentration is too low, the amount of adhesion decreases, making it impossible to obtain a sufficient effect. Next, the invention described in claim 2 (second claim)
Invention) will be explained in more detail. In the second invention, adhesion is improved by treating the rubber reinforcing fibers using a second liquid containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent instead of the second liquid of the first invention. Since the other constituent features of the second invention are the same as those of the first invention, only the vulcanizing agent will be explained below. Vulcanizing agents include polynitroso aromatic compounds (e.g. p-dinitrosobenzene), tetrachlorobenzoquinone, polyp-dinitrosobenzene, p,
p'-dibenzoyl, benzoquinone dioxime, p
-benzoquinone dioxime is exemplified, and tetrachlorobenzoquinone, poly p-dinitrosobenzene, p,p'-dibenzoylbenzoquinone dioxime, and p-benzoquinone dioxime are particularly preferred. It is appropriate that the amount of the vulcanizing agent in the second liquid is 0.3 to 2 wt%, preferably about 0.6 to 1 wt%; if this amount is too small, the effect will not be sufficient, and the Peeling between the liquid layer and the liquid layer is likely to occur. Also, if this amount is too large, the rubber matrix and
Peeling from the liquid layer is likely to occur. Next, the invention described in claim 3 (third claim)
Invention) will be explained in more detail. In the third invention, the water resistance is improved by treating the rubber reinforcing fibers using a second liquid containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent instead of the second liquid of the second invention. Other constituent features of the third invention are the same as those of the second invention, so only the lead compound will be explained below. Lead compounds include litharge, lead maleate,
Particularly preferred is lead phthalate. The amount of lead compound in the second liquid is suitably 0.5 to 5 wt%, preferably 1 to 3 wt%. Although there are no particular limitations on the reinforcing fibers to be treated by the methods of the first, second, and third inventions (hereinafter collectively referred to as the present invention), it is practical to use glass fibers. For example, about 200 glass fibers with a thickness of 9 μm added with a sizing agent and bundled can be suitably used. Three such reinforcing fibers are arranged and 12 to 22 wt%, preferably 16 to 20 wt% of the first liquid is applied thereto according to a conventional method. After applying the first liquid, preferably after sufficiently drying,
Apply the second liquid according to the usual method. Drying of the first liquid
It is desirable to carry out at 200-350℃. The amount of the second liquid applied is 0.5 to 5wt% based on the reinforcing fibers.
A suitable content is desirably 2 to 4 wt%. After applying the second liquid, it is preferably dried at 120 to 200°C. In addition, 2.54
After applying an S or Z twist (pre-twist) of about 0.5 to 4.0 per cm (1 strand), pull together about 2 to 13 more strands and twist in the opposite direction to the pre-twist, about 0.5 to 3.0 per 2.54 cm. It is desirable to apply the second liquid to the yarn by giving it a ply twist. There is no particular limitation on the type of rubber to be reinforced with the reinforcing fibers to which the treatment agent of the present invention has been applied, but Hypalon, nitrile rubber, hydrogenated nitrile rubber, etc. can be used as examples, and very suitable results can be obtained, and heat resistance , reinforced rubber products such as timing belts with good durability can be obtained. (Function) The first liquid of the present invention has good affinity with the reinforcing fibers, and forms a first layer firmly adhered to the reinforcing fibers. The second liquid has insufficient adhesion to the reinforcing fibers, but is reactive with the first liquid, and the second layer formed by the second liquid is integrated with the first layer, and the second layer is integrated with the first layer. It is firmly bonded to reinforcing fibers through one layer. and the second
It is believed that the layer is compatible with the rubber matrix and will bond strongly with the rubber matrix to provide favorable results. Further, in the second invention, adhesion is improved by adding a vulcanizing agent to the second liquid, and further, in the third invention, water resistance is also improved by adding a lead compound to the second liquid. Example 1 Vinylpyridine, styrene and butadiene
Vinylpyridine-styrene-butadiene terpolymer latex (Pyratex, trade name, manufactured by Sumitomo Naugatatsu Co., Ltd., terpolymer content 41wt%) containing in a ratio of 15:15:70, 65 parts by weight, butadiene latex (0700) , trade name, Nippon Synthetic Rubber Co., Ltd., butadiene content: 57 wt%), 8 parts by weight, an aqueous solution containing 20 wt% of an addition condensate of resorcinol and formaldehyde (resol), to a mixture of 15 parts by weight and 12 parts by weight of water, and further A first liquid was obtained by adding 1 part by weight of a mineral oil emulsion (mineral oil content: 55 wt%) and 1 part by weight of aqueous ammonia (concentration: 18 wt%) as anti-aging agents. Add 10 parts of chlorosulfonylated polyethylene (Hypalon 40, trade name, manufactured by Showa Neoprene Co., Ltd.), 5 parts of polyisocyanate (MR-200, trade name, manufactured by Nippon Polyurethane Co., Ltd.), and doluene to adjust the concentration.
A 10wt% second liquid was obtained. The first liquid was applied to three glass fiber bundles, each consisting of 200 9μ glass fibers, in a conventional manner. (Solid content 17wt%). After drying at 250℃ for 1 minute, this glass fiber bundle was given 4.0 Z twists (first twist) per 2.54 cm, and the fiber bundle that had been given this first twist was further twisted.
2.1 turns of S twist per 2.54 cm (ply twist) of 13 strands
The second solution was added to the sample. (solid content 3%)
This was dried at 130°C for 1 minute and used as a reinforcing fiber to prepare a test piece. Type of rubber: 100 parts by weight of hydrogenated nitrile rubber: 40 parts by weight of carbon black, 5 parts by weight of zinc white, 1 part by weight of stearic acid, 2 parts by weight of anti-aging agent, 3 parts by weight of vulcanization accelerator, 5 parts by weight of plasticizer. A combination of. Test piece 1 Two of the above reinforcing fibers were sandwiched between rubber sheets with a thickness of 1 mm, a width of 5 mm, and a length of 300 mm, pressed, and heated at 150°C.
Vulcanized for 20 minutes Test piece 2 The reinforcing fibers were lined up without gaps between rubber sheets with a thickness of 3 mm, width of 25.4 mm, and length of 100 mm, pressed, and vulcanized for 20 minutes at 150°C. Tensile strength of this test piece The strength and this test piece 1
After being left in an oven at 120°C for 24 hours, the tensile strength of test piece 1 was measured using an MIT tester after applying bending stress 3000 times. This test piece 2 and the test piece left in hot water at 100°C for 1 hour were measured using an autograph at 50°C.
The adhesive force was measured by peeling at a drawing speed of mm/min. The above test results are shown in the attached table. Example 2 Instead of the rubber in Example 1, 50 parts by weight of carbona black, 10 parts by weight of MgO, 10 parts by weight of plasticizer, 1 part by weight of anti-aging agent, and 2 parts by weight of vulcanization accelerator were added to 100 parts by weight of Hypalon. The results of a test similar to that of Example 1 using the blended product are shown in the attached table. Example 3 Vinylpyridine, styrene and butadiene
Vinylpyridine-styrene-butadiene terpolymer latex (Pyratex, trade name, manufactured by Sumitomo Naugatatsu Co., Ltd., terpolymer content 41wt%) containing in a ratio of 15:15:70, 65 parts by weight, butadiene latex (0700) , trade name, Japan Synthetic Rubber Co., Ltd., butadiene content: 57 wt%), 8 parts by weight, an aqueous solution containing 20 wt% of an addition condensate of resorcinol and formaldehyde (resol), to a mixture of 15 parts by weight and 12 parts by weight of water, and then A first liquid was obtained by adding 1 part by weight of a mineral oil emulsion (mineral oil content: 55 wt%) and 1 part by weight of aqueous ammonia (concentration: 18 wt%) as anti-aging agents. Chlorosulfonylated polyethylene (Hypalon 40, trade name, manufactured by Showa Neoprene Co., Ltd.) 10 parts, polyisocyanate (MR-200, trade name, manufactured by Nippon Polyurethane Co., Ltd.) 5 parts, p,p'-dibenzoylbenzoquinone dioxime 2 A second liquid with a concentration of 10 wt% was obtained by adding 100% of doluene. The first liquid was applied to three glass fiber bundles, each consisting of 200 9μ glass fibers, in a conventional manner. (Solid content 17wt%). After drying at 250℃ for 1 minute, this glass fiber bundle was given 4.0 Z twists (pre-twist) per 2.54 cm, and the fiber bundle with this pre-twist was further twisted.
2.1 turns of S twist per 2.54 cm (ply twist) of 13 strands
The second solution was added to the sample. (Solid 3
%) This was dried at 130°C for 1 minute and used as a reinforcing fiber to prepare a test piece. Type of rubber: 100 parts by weight of hydrogenated nitrile rubber: 40 parts by weight of carbon black, 5 parts by weight of zinc white, 1 part by weight of stearic acid, 2 parts by weight of anti-aging agent, 3 parts by weight of vulcanization accelerator, 5 parts by weight of plasticizer. A combination of. Test piece 1 Two of the above reinforcing fibers were sandwiched between rubber sheets with a thickness of 1 mm, a width of 5 mm, and a length of 300 mm, pressed, and heated at 150°C.
Vulcanized for 20 minutes Test piece 2 The above reinforcing fibers were arranged without gaps between rubber sheets with a thickness of 3 mm, width of 25.4 mm, and length of 100 mm, pressed, and heated at 150°C for 20 minutes.The tensile strength of this test piece was The strength and this test piece 1
After being left in an oven at 120°C for 24 hours, the tensile strength of test piece 1 was measured using an MIT tester after applying bending stress 3000 times. This test piece 2 and the test piece left in hot water at 100°C for 1 hour were measured using an autograph at 50 mm/
The adhesive force was measured by peeling at a pulling speed of min. The above test results are shown in the attached table. Example 4 Instead of the rubber in Example 3, 50 parts by weight of carbon black, 10 parts by weight of MgO, 10 parts by weight of plasticizer, 1 part by weight of anti-aging agent, and 2 parts by weight of vulcanization accelerator were blended with 100 parts by weight of Hypalon. The results of a test similar to that of Example 1 are shown in the attached table. Examples 5 and 6 Tetrachlorobenzoquinone was used instead of p-p'dibenzoylbenzoquinone dioxime in the second liquid of Examples 3 and 4, and a second liquid containing 2 wt% of Lissage was used, and Example 1 I did a similar test. The results are shown in the attached table. Comparative Examples 1 and 2 Using reinforcing fibers coated with 20wt% of the same first liquid as in Example 1, test pieces similar to those in Examples 1 and 2 were prepared and the same tests were conducted. The results are shown in the attached table. Comparative Examples 3 and 4 In place of the first liquid in Comparative Examples 1 and 2, the same second liquid as in Example 1 was used, test pieces similar to those in Examples 1 and 2 were prepared, and the same tests were conducted. The results are shown in the attached table. Comparative Examples 5 and 6 In place of the first liquid in Comparative Examples 1 and 2, the same second liquid as in Example 3 was used, test pieces similar to those in Examples 1 and 2 were prepared, and the same tests were conducted. The results are shown in the attached table. Comparative Examples 7 and 8 In place of the first liquid in Comparative Examples 1 and 2, the same second liquid as in Example 5 was used, test pieces similar to those in Examples 1 and 2 were prepared, and the same tests were conducted. The results are shown in the attached table.
【表】
ゴム、ハイパロンを示す。
（発明の効果）
本発明の方法で処理された補強繊維はハイパロ
ン、水素添加ニトロゴム等の耐熱ゴムに対する接
着力が大きく、又屈曲強度の大きいゴム製品が得
られる。又本発明の処理液はポツトライフも30日
程度と極めて大きい。[Table] Rubber and Hypalon are shown.
(Effects of the Invention) The reinforcing fibers treated by the method of the present invention have a high adhesive strength to heat-resistant rubbers such as Hypalon and hydrogenated nitro rubber, and a rubber product with high bending strength can be obtained. Furthermore, the treatment solution of the present invention has an extremely long pot life of about 30 days.
Claims (1)
ターポリマーラテツクス、ゴムラテツクス及びレ
ゾルジン−ホルムアルデヒドの水溶性縮合物を含
む第１液で処理した後、ハロゲン含有ポリマー、
イソシアネートを含む第２液で処理することを特
徴とするゴム補強用繊維の処理方法。 ２ ゴムラテツクスはブタジエンラテツクスであ
ることを特徴とする特許請求の範囲第１項記載の
ゴム補強用繊維の処理方法。 ３ ハロゲン含有ポリマーはクロロスルフオニル
化ポリエチレンであることを特徴とする特許請求
の範囲第１項又は第２項記載のゴム補強用繊維の
処理方法。 ４ ビニールピリジン−スチレン−ブタジエンの
ターポリマーラテツクス、ゴムラテツクス及びレ
ゾルジン−ホルムアルデヒドの水溶性縮合物を含
む第１液で処理した後、ハロゲン含有ポリマー、
イソシアネート及び加硫剤を含む第２液で処理す
ることを特徴とするゴム補強用繊維の処理方法。 ５ 加硫剤はテトラクロロベンゾキノン、ｐ，
p′−ジベンゾイルベンゾキノンジオキシム又はｐ
−ベンゾキノンジオキシムでることを特徴とする
特許請求の範囲第４項記載のゴム補強用繊維の処
理方法。 ６ ビニールピリジン−スチレン−ブタジエンの
ターポリマーラテツクス、ゴムラテツクス及びレ
ゾルジン−ホルムアルデヒドの水溶性縮合物を含
む第１液で処理した後、ハロゲン含有ポリマー、
イソシアネート、加硫剤及び鉛化合物を含む第２
液で処理することを特徴とするゴム補強用繊維の
処理方法。 ７ 加硫剤はテトラクロロベンゾキノン、ｐ，
p′−ジベンゾイルベンゾキノンジオキシム又はｐ
−ベンゾキノンジオキシムでることを特徴とする
特許請求の範囲第６項記載のゴム補強用繊維の処
理方法。[Scope of Claims] 1. After being treated with a first liquid containing a terpolymer latex of vinyl pyridine-styrene-butadiene, a rubber latex, and a water-soluble condensate of resordine-formaldehyde, a halogen-containing polymer,
A method for treating rubber reinforcing fibers, comprising treating with a second liquid containing an isocyanate. 2. The method for treating rubber reinforcing fibers according to claim 1, wherein the rubber latex is butadiene latex. 3. The method for treating rubber reinforcing fibers according to claim 1 or 2, wherein the halogen-containing polymer is chlorosulfonylated polyethylene. 4 After treatment with a first liquid containing a vinyl pyridine-styrene-butadiene terpolymer latex, a rubber latex and a water-soluble condensate of resordine-formaldehyde, a halogen-containing polymer,
A method for treating rubber reinforcing fibers, comprising treating with a second liquid containing an isocyanate and a vulcanizing agent. 5 The vulcanizing agent is tetrachlorobenzoquinone, p,
p′-dibenzoylbenzoquinone dioxime or p
- The method for treating rubber reinforcing fibers according to claim 4, characterized in that benzoquinone dioxime is used. 6 After treatment with a first liquid containing a vinyl pyridine-styrene-butadiene terpolymer latex, a rubber latex and a water-soluble condensate of resordine-formaldehyde, a halogen-containing polymer,
A second compound containing isocyanates, vulcanizing agents and lead compounds.
A method for processing rubber reinforcing fibers, characterized by processing with a liquid. 7 The vulcanizing agent is tetrachlorobenzoquinone, p,
p′-dibenzoylbenzoquinone dioxime or p
- A method for treating rubber reinforcing fibers as claimed in claim 6, characterized in that benzoquinone dioxime is used.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26979786A JPS63126975A (en) | 1986-11-14 | 1986-11-14 | Treatment of rubber reinforcing fiber |
| JP2308568A JPH03170534A (en) | 1986-11-14 | 1990-11-16 | Method for treating glass fiber for reinforcing rubber, and preparation of reinforced rubber product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26979786A JPS63126975A (en) | 1986-11-14 | 1986-11-14 | Treatment of rubber reinforcing fiber |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2308568A Division JPH03170534A (en) | 1986-11-14 | 1990-11-16 | Method for treating glass fiber for reinforcing rubber, and preparation of reinforced rubber product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126975A JPS63126975A (en) | 1988-05-30 |
| JPH024715B2 true JPH024715B2 (en) | 1990-01-30 |
Family
ID=17477296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26979786A Granted JPS63126975A (en) | 1986-11-14 | 1986-11-14 | Treatment of rubber reinforcing fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63126975A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0777066A3 (en) * | 1995-10-30 | 1998-01-07 | Bando Chemical Industries, Limited | Tension member for belt, method of producing the same and belt including the same |
| WO2007114228A1 (en) | 2006-03-31 | 2007-10-11 | Central Glass Company, Limited | Coating liquid for coating glass fiber and rubber-reinforcing glass fiber using the same |
| US9091325B2 (en) | 2004-10-01 | 2015-07-28 | Central Glass Company, Limited | Coating liquid for covering glass fiber and rubber-reinforcing glass fiber using same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2625421B2 (en) * | 1986-11-26 | 1997-07-02 | 日本硝子繊維 株式会社 | Glass fiber cord |
| JPH01272876A (en) * | 1988-04-19 | 1989-10-31 | Mitsuboshi Belting Ltd | Fiber for reinforcing rubber and toothed belt using said fiber |
| JPH03269178A (en) * | 1990-03-20 | 1991-11-29 | Asahi Fiber Glass Co Ltd | Rubber reinforcing fiber |
| JP2894799B2 (en) * | 1990-06-27 | 1999-05-24 | 日本硝子繊維株式会社 | Glass fiber for rubber reinforcement |
| JP3864097B2 (en) | 2001-03-12 | 2006-12-27 | 本田技研工業株式会社 | Fiber for reinforcing rubber products |
| JP4030499B2 (en) | 2003-01-22 | 2008-01-09 | セントラル硝子株式会社 | Glass fiber for rubber reinforcement |
| JP2005009010A (en) | 2003-06-18 | 2005-01-13 | Asahi Fiber Glass Co Ltd | Reinforcing fiber for rubber product |
| KR101181128B1 (en) | 2004-06-28 | 2012-09-14 | 니혼 이타가라스 가부시키가이샤 | Cord for reinforcing rubber, method of manufacturing the cord, and rubber product using the cord |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4914546A (en) * | 1972-03-22 | 1974-02-08 | ||
| JPS5136247A (en) * | 1974-05-31 | 1976-03-27 | Uniroyal Inc | |
| JPS55114551A (en) * | 1979-02-23 | 1980-09-03 | Gen Tire & Rubber Co | Adhesion of glass fiber to rubber |
-
1986
- 1986-11-14 JP JP26979786A patent/JPS63126975A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4914546A (en) * | 1972-03-22 | 1974-02-08 | ||
| JPS5136247A (en) * | 1974-05-31 | 1976-03-27 | Uniroyal Inc | |
| JPS55114551A (en) * | 1979-02-23 | 1980-09-03 | Gen Tire & Rubber Co | Adhesion of glass fiber to rubber |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0777066A3 (en) * | 1995-10-30 | 1998-01-07 | Bando Chemical Industries, Limited | Tension member for belt, method of producing the same and belt including the same |
| US9091325B2 (en) | 2004-10-01 | 2015-07-28 | Central Glass Company, Limited | Coating liquid for covering glass fiber and rubber-reinforcing glass fiber using same |
| WO2007114228A1 (en) | 2006-03-31 | 2007-10-11 | Central Glass Company, Limited | Coating liquid for coating glass fiber and rubber-reinforcing glass fiber using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63126975A (en) | 1988-05-30 |
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