JPH02221466A - Treating solution for rubber reinforcing fiber and treatment of rubber reinforcing fiber - Google Patents
Treating solution for rubber reinforcing fiber and treatment of rubber reinforcing fiberInfo
- Publication number
- JPH02221466A JPH02221466A JP3605689A JP3605689A JPH02221466A JP H02221466 A JPH02221466 A JP H02221466A JP 3605689 A JP3605689 A JP 3605689A JP 3605689 A JP3605689 A JP 3605689A JP H02221466 A JPH02221466 A JP H02221466A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- latex
- reinforcing fiber
- butadiene
- rubber reinforcing
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000005060 rubber Substances 0.000 title claims abstract description 50
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 29
- 229920000126 latex Polymers 0.000 claims abstract description 50
- 239000004816 latex Substances 0.000 claims abstract description 45
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229920001897 terpolymer Polymers 0.000 claims abstract description 16
- 229920002681 hypalon Polymers 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 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 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 51
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 238000005452 bending Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920003051 synthetic elastomer 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
- USDNTLSSMWDFHG-UHFFFAOYSA-N 2-ethenylpyridine;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 USDNTLSSMWDFHG-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XYLFFOSVQCBSDT-UHFFFAOYSA-N 1,2-dinitrosobenzene Chemical compound O=NC1=CC=CC=C1N=O XYLFFOSVQCBSDT-UHFFFAOYSA-N 0.000 description 1
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KMGMCLWJFCGWFI-UHFFFAOYSA-N chembl3276923 Chemical compound ON=C1C=CC(=O)C=C1 KMGMCLWJFCGWFI-UHFFFAOYSA-N 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- 239000000463 material Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、ゴム補強繊維用処理液並びにゴム補強用繊維
の処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a treatment liquid for rubber reinforcing fibers and a method for treating rubber reinforcing fibers.
[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
、ガラスミmヤーン等の補強amが広く用いられる。[Prior Art] In order to increase the strength of rubber products such as rubber belts and tires, reinforcing am such as glass fiber m yarn is widely used.
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、補強材とゴムマトリッ
クスの間に剥離が生じ易い。Rubber products such as rubber belts are subjected to repeated bending stress, resulting in bending fatigue, resulting in decreased performance, and peeling between the reinforcing material and the rubber matrix is likely to occur.
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。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.
処理剤としては各種組成のものが提案されている。Various compositions of processing agents have been proposed.
例えばビニルピリジン−スチレン−ブタジエンのターポ
リマーラテッ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、或はゴムラテックスを添加し
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)。For example, various processing agents have been proposed, such as a processing agent using a combination of vinylpyridine-styrene-butadiene terpolymer latex and a water-soluble condensate of resorcinol and formalin, or a processing agent containing rubber latex (Japanese Unexamined Patent Application Publication No. 1983-1992).
114551).
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)。Also, polyisocyanates, polynitroso aromatic compounds,
A treatment liquid containing an acidic halogen-containing polymer has also been proposed (see Japanese Patent Laid-Open No. 14546/1983).
又、ゴム補強用繊維にレゾルシンホルムアルデヒドの水
溶性縮合物及びゴムラテックスを含む第1液(RFL液
)を塗布して該繊維上にレゾルシンホルムアルデヒド縮
合物及びゴムを含む第1層を形成させ、次いでゴムラテ
ックス及びイソシアネートを含むオーバーコート液で処
理し、イソシアネート及びゴムを含む第2層を形成させ
ることも知られている(特開昭49−14546号公報
参照)。Further, a first liquid (RFL liquid) containing a water-soluble condensate of resorcin formaldehyde and rubber latex is applied to the rubber reinforcing fibers to form a first layer containing the resorcin formaldehyde condensate and rubber on the fibers, and then It is also known to treat with an overcoat liquid containing rubber latex and isocyanate to form a second layer containing isocyanate and rubber (see JP-A-49-14546).
[発明が解決しようとする課題]
従来のゴム補強繊維用処理液並びにゴム補強用繊維の処
理方法は次のような問題点を有する。[Problems to be Solved by the Invention] Conventional treatment liquids for rubber reinforcing fibers and conventional methods for treating rubber reinforcing fibers have the following problems.
(1)充分な接着力が得られない。(1) Sufficient adhesive strength cannot be obtained.
(2)充分な屈曲強度を有するゴム製品が得難い。(2) It is difficult to obtain rubber products with sufficient bending strength.
(3)高温で使用すると接着性が低下する。即ち、耐熱
性が不充分である。(3) Adhesiveness decreases when used at high temperatures. That is, heat resistance is insufficient.
近時、自動用のエンジン付近の温度上昇に伴い、タイミ
ングベルト用のゴムとして、クロロスルフォニル化ポリ
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って来たが、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、長距離走行に耐え
るタイミングベルトは得られていない。Recently, with the rise in temperature near automobile engines, heat-resistant rubbers such as chlorosulfonylated polyethylene and hydrogenated nitrile rubber have come to be used as rubber for timing belts. Since such heat-resistant rubber has lower adhesion than ordinary rubber, the above-mentioned drawbacks tend to be greater than that of ordinary rubber, and a timing belt that can withstand long-distance running has not been obtained.
RFL液でゴム補強用繊維を処理し、次いで、ゴムラテ
ックス及びイソシアネートを含むオーバーコート液で処
理することにより、上述の問題点を成る程度解消するこ
とはできるが、この方法は次のような問題点を有する。Although the above-mentioned problems can be overcome to some extent by treating the rubber reinforcing fibers with an RFL liquid and then with an overcoat liquid containing rubber latex and isocyanate, this method has the following problems. Has a point.
(1)接着力が時間経過とともに低下する。(1) Adhesive strength decreases over time.
(2)充分な効果をつるためには多量のイソシアネート
を使用する必要があり、イソシアネートの量を増大させ
ると液の安定性が悪化し、オーバーコート液を使用の都
度少量づつ調整する必要がある。(2) It is necessary to use a large amount of isocyanate in order to obtain a sufficient effect; increasing the amount of isocyanate deteriorates the stability of the solution, and it is necessary to adjust the overcoat solution in small amounts each time it is used. .
(3)RFL層(第1層)とオーバーコート液(第2層
)の間の界面接着性が悪く、第1゜2層間に剥離が生じ
易い。(3) The interfacial adhesion between the RFL layer (first layer) and the overcoat liquid (second layer) is poor, and peeling easily occurs between the first and second layers.
本発明は、上述の従来技術の問題点を解消し、繰返し屈
曲応力を受けるような条件下で使用していても、時間の
経過とともに接着力が低下することなく、耐熱性の大き
いゴム補強繊維用処理液(RFL液)並びにこの処理液
で処理した後、以下詳述するようなオーバーコート液で
ゴム補強用繊維を処理することにより、上記特性を一層
向上させ得るようにゴム補強繊維用の処理方法を提供す
ることを目的とする。The present invention solves the above-mentioned problems of the prior art, and provides rubber reinforcing fibers with high heat resistance that do not reduce adhesive strength over time even when used under conditions of repeated bending stress. By treating the rubber reinforcing fibers with a treatment liquid (RFL liquid) and an overcoat liquid as described in detail below, the rubber reinforcing fibers can be further improved. The purpose is to provide a processing method.
[課題を解決するための手段]
上記目的を達成するために、本発明においては、ビニル
ピリジン−スチレン−ブタジェンのターポリマーラテッ
クス又はブタジェン系ラテックス、マロロスルフオン化
ボリエ、チレンラテッ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ゴム補強繊維用処理液をゴム
補強繊維の処理に用い、又ビニルピリジン−スチレン−
ブタジェンのターポリマーラテックス又はブタジェン系
ラテックス、クロロスルフォン化ポリエチレンラテック
ス及びレゾルシンホルムアルデヒドのを含む第1液で処
理した後、加硫剤、鉛化合物、イソシアネート及びハロ
ゲン含有ポリマーを含むオーバーコート液で処理するゴ
ム補強用tagを処理する。[Means for Solving the Problems] In order to achieve the above object, the present invention uses a water-soluble condensation of a vinylpyridine-styrene-butadiene terpolymer latex or a butadiene-based latex, malolosulfonated bolyene, tyrene latex, and resorcin formaldehyde. A treatment liquid for rubber reinforcing fibers containing vinyl pyridine-styrene is used to treat rubber reinforcing fibers.
Rubber treated with a first liquid containing a terpolymer latex of butadiene or a butadiene-based latex, a chlorosulfonated polyethylene latex and resorcin formaldehyde, and then treated with an overcoat liquid containing a vulcanizing agent, a lead compound, an isocyanate and a halogen-containing polymer. Process the reinforcement tag.
次に本発明を更に具体的に説明する。Next, the present invention will be explained in more detail.
レゾルシンホルムアルデヒドの水溶性縮合物(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
ゾルシンとホ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。A water-soluble condensate of resorcin formaldehyde (hereinafter simply referred to as a condensate) is a resorcin and formaldehyde rich in oxymethyl groups obtained by reacting resorcin and formaldehyde in the presence of an alkaline catalyst such as an alkali hydroxide, ammonia, or an amine. Water-soluble initial addition condensates (resols) can be preferably used. In particular, the molar ratio of resorcin and formaldehyde is 1:0.3 to 2.
.. It is preferable to react at a ratio of 5:5 to 5:5.
第1液において使用されるゴムラテックスとしては、ゴ
ム補強用繊維用処理剤として使用される比較的低重度の
ラテックスが好適に使用でき、限定はないが、特にブタ
ジェンゴムラテックス、ビニルピリジン−スチレン−ブ
タジェンのターポリマーラテックス(以下ターポリマー
ラテックスという)就中、ターポリマーラテックスが好
ましい。As the rubber latex used in the first liquid, a relatively low-heavy latex used as a treatment agent for rubber reinforcing fibers can be suitably used, and there is no limitation, but in particular, butadiene rubber latex, vinylpyridine-styrene, etc. - Terpolymer latex of butadiene (hereinafter referred to as terpolymer latex) is preferred.
ビニルピリジン−スチレン−ブタジエンのターポリマー
ラテックス(以下ターポリマーラテックスと呼ぶ)とし
てはビニルピリジン、スチレン、ブタジェンの重量割合
がlO〜20:10〜20:60〜80のものが特に適
当であり、Pyratex(商品名、住人ノーガタック
社製) 、 0650 (商品名1日本合成ゴム製)
、 N1pol 2518FS (商品名。As the vinylpyridine-styrene-butadiene terpolymer latex (hereinafter referred to as terpolymer latex), one in which the weight ratio of vinylpyridine, styrene, and butadiene is 10 to 20:10 to 20:60 to 80 is particularly suitable. (Product name, Manufactured by Naugatuck Co., Ltd.), 0650 (Product name 1, Manufactured by Japan Synthetic Rubber)
, N1pol 2518FS (product name.
日本ゼオン製)等が好適に使用できる。(manufactured by Nippon Zeon) etc. can be suitably used.
又ブタジェン系ラテックスとしては、ブタジェンラテッ
クス、ブタジェン−スチレンの共重合体ラテックス等が
適当であり、0700 (商品名、日本合成ゴム製)
、 N1pol LXIII (商品名日本ゼオン製
)等が好適に使用できる。As the butadiene latex, butadiene latex, butadiene-styrene copolymer latex, etc. are suitable, such as 0700 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.).
, N1pol LXIII (trade name manufactured by Nippon Zeon), etc. can be suitably used.
上記ターポリマーラテックス、ブタジェン系ラテックス
はその一方のみを以下述べるCSMラテックス 及び縮
合物と混合してもよいが1両者を併用しCSMラテック
ス及び縮合物と混合するのが好ましい。Although only one of the above terpolymer latex and butadiene latex may be mixed with the CSM latex and condensate described below, it is preferable to use both in combination and mix with the CSM latex and condensate.
クロロスルフォン化ポリエチレン(CSM)ラテックス
としては、塩素含有量20〜40wt%好ましくは25
〜35wt%、スルフォン基中のS含有量は0.5〜2
.0豐t%好ましくは1.1〜1.4豐t%のものが適
当であり、生ゴムのムーニー粘度が30〜95のものが
好適に使用できる。The chlorosulfonated polyethylene (CSM) latex has a chlorine content of 20 to 40 wt%, preferably 25
~35wt%, S content in sulfone group is 0.5~2
.. A raw rubber having a Mooney viscosity of 30 to 95 is suitable.
なお、CSMラテックスの一部(50wt%以下、好ま
しくは25wt%以下)をクロロプレン(CR)又は水
素二トリルゴム(H−NBR)のラテックスで置換する
こともできる。Note that a part of the CSM latex (50 wt% or less, preferably 25 wt% or less) can also be replaced with a latex of chloroprene (CR) or hydrogen nitrile rubber (H-NBR).
上述の各成分を含むゴム補強mMI用処理液(第1液)
中のターポリマーラテックス、又はブタジェン系ラテッ
クス、CSMラテックス、縮合物の濃度は夫々10〜3
0wt%、3〜25wt%、0.5〜6wt%好ましく
は15〜25wt%、5〜15wt%、1〜3wt%、
2〜6wt%とじてこれらの合計量は10〜50wt%
、好ましくは20〜40wt%とし、又補強繊維に対す
る第1液の付与量は固型分としてm維重量の12〜25
wt%、好ましくは16〜22wt%とするのが適当で
ある。Rubber reinforcing mmI treatment liquid (first liquid) containing each of the above-mentioned components
The concentration of the terpolymer latex, butadiene latex, CSM latex, and condensate inside is 10 to 3, respectively.
0 wt%, 3-25 wt%, 0.5-6 wt%, preferably 15-25 wt%, 5-15 wt%, 1-3 wt%,
The total amount of these is 10 to 50 wt% including 2 to 6 wt%.
, preferably 20 to 40 wt%, and the amount of the first liquid applied to the reinforcing fibers is 12 to 25 m fiber weight as solid content.
A suitable amount is 16 to 22 wt%, preferably 16 to 22 wt%.
なお、第1液中には、必要に応じラテックスの安定剤、
老化防止剤等を添加することも出来る。The first liquid may contain a latex stabilizer, if necessary.
It is also possible to add anti-aging agents and the like.
次にオーバーコート液に就いて説明する。Next, the overcoat liquid will be explained.
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、クロロスルフォン化
ポリエチレン等が使用できるがクロロスルフォン化ポリ
エチレンが特に好適な結果を与える。As the halogen-containing polymer, chlorinated rubber, chloroprene, chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated polyvinyl chloride, chlorosulfonated polyethylene, etc. can be used, but chlorosulfonated polyethylene gives particularly favorable results. .
クロロスルフォン化ポリエチレン(CSM)ラテックス
としては、塩素含有量20〜40wt%好ましくは25
〜35wt%、スルフォン基中のS含有量は0.5〜2
.Owt%好ましくは1.1〜1.4 wt%のものが
適当であり、生ゴムのムーニー粘度が30〜95のもの
が好適に使用できる。The chlorosulfonated polyethylene (CSM) latex has a chlorine content of 20 to 40 wt%, preferably 25
~35wt%, S content in sulfone group is 0.5~2
.. Owt% is preferably 1.1 to 1.4 wt%, and raw rubber having a Mooney viscosity of 30 to 95 can be suitably used.
又、オーバーコート液中のハロゲン含有ポリマーの量は
、固型分として1〜10wt%、好ましくは2〜5wt
%とするのが適当である。この量があまり少ないと、本
発明の効果が充分ではなく、この量があまり多いと接着
力が低下しい。Further, the amount of halogen-containing polymer in the overcoat liquid is 1 to 10 wt%, preferably 2 to 5 wt% as solid content.
% is appropriate. If this amount is too small, the effect of the present invention will not be sufficient, and if this amount is too large, the adhesive strength will tend to decrease.
オーバーコート液中には、インシアネートを添加する。Incyanate is added to the overcoat liquid.
イソシアネートの量は、0.5〜2.Owt%、好まし
くは1〜1.5 wt%とするのが適当であり、接着性
を向上させることができる。The amount of isocyanate is between 0.5 and 2. Owt%, preferably 1 to 1.5 wt%, is suitable and can improve adhesiveness.
イソシアネートの量は、従来技術の約50%程度で充分
であり、インシアネートを過剰に用いた場合に生ずる屈
曲疲労性、並びに耐熱性の悪化が生ずることもなく、又
オーバーコート液の安定性が増大する。The amount of isocyanate is about 50% of that of the conventional technology, which is sufficient, and there is no deterioration in bending fatigue or heat resistance that would occur if inocyanate is used in excess, and the stability of the overcoat liquid is improved. increase
オーバーコート液中のイン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〜lO冑t%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、
この濃度があまり小さいと付着量が減少し、充分な効果
が得られなくなる。The weight percent of the total amount of incyanate and halogen-containing polymer in the overcoat liquid is suitably 3 to 15 wt%, preferably 5 to 10% by weight; if this concentration is too large, the viscosity of the liquid will increase. As a result, unevenness is likely to occur,
If this concentration is too small, the amount of adhesion will decrease and a sufficient effect will not be obtained.
更に又、オーバーコート液中には加硫剤及び鉛化合物を
含有せしめることにより、更に接着性並びに耐水性を向
上さる。Furthermore, by containing a vulcanizing agent and a lead compound in the overcoat liquid, the adhesiveness and water resistance are further improved.
加硫剤としてはポリニトロソ芳香族化合物A(例えばp
−ジニトロソベンゼン)、テトラクロロペンゾキソン、
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−ベンゾキノンオキシム
が例示されるが、テトラクロロペンゾキソン、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。As a vulcanizing agent, a polynitroso aromatic compound A (for example, p
- dinitrosobenzene), tetrachloropenzoxon,
Examples include poly p-dinitrosobenzene, p, p'-dibenzoyl, benzoquinone dioxime, p-benzoquinone oxime, and tetrachloropenzoxon, poly p-
Particularly preferred are dinitrosobenzene, p,p-dibenzoylbenzoquinone dioxime, and p-benzoquinone dioxime.
オーバーコート液中の加硫剤の量は0.3〜3wt%、
望ましくは0.6〜2.5 wt%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液層との間に剥離が生じ易くなる。The amount of vulcanizing agent in the overcoat liquid is 0.3 to 3 wt%,
Desirably, it is appropriate to set the amount to about 0.6 to 2.5 wt%; if this amount is too small, the effect will not be sufficient and separation will easily occur between the first liquid layer and the second liquid layer. .
又この量があまり多いとゴムマトリックスと第2液層と
の剥離が生じ易くなる。Moreover, if this amount is too large, peeling between the rubber matrix and the second liquid layer tends to occur.
鉛化合物としては、リサージ、マレイン酸鉛。Lead compounds include litharge and lead maleate.
フタル酸鉛が適当であり、オーバーコート液中の鉛化合
物の量は0.5〜5wt%、好ましくは1〜3wt%と
するのが適当である。Lead phthalate is suitable, and the amount of lead compound in the overcoat solution is suitably from 0.5 to 5 wt%, preferably from 1 to 3 wt%.
本発明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0例えば
、太さ91Lのガラス繊維に集束剤を付与して206本
程度集束したガラス繊維が好適に使用できる。The reinforcing fibers to be treated by the method of the present invention are not particularly limited, but it is practical to use glass fibers. Glass fiber can be suitably used.
このような補強繊維を3本引揃え、これに第1液を12
〜25wt%望ましくは16〜22wt%常法に従い塗
布する。Arrange three such reinforcing fibers and add 12 ml of the first liquid to them.
~25 wt%, preferably 16~22 wt%, applied according to a conventional method.
第1液を付与後好ましくは充分乾燥させた後。After applying the first liquid, preferably after sufficiently drying.
オーバーコート液を常法に従い塗布する。第1液の乾燥
は200〜350℃で行うのが望ましい。Apply overcoat liquid according to the usual method. It is desirable to dry the first liquid at 200 to 350°C.
オーバーコート液の塗布量は補強繊維に対し、O,S〜
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°C
において乾燥する。The amount of overcoat liquid applied is O, S to reinforcing fibers.
A suitable amount is 5 wt%, preferably 2 to 4 wt%. Preferably at 120-200°C after applying the second liquid
Dry in .
なお−上述の第1液を塗布した補強繊維に2.54cm
(1インチ)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木程度引揃えて
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。Note: 2.54 cm of reinforcing fiber coated with the above first liquid
(1 inch) of S or Z twist (pre-twist) of about 0.5 to 4.0 per inch is further arranged around 2 to 13 pieces to create a twist of about 0.5 to 3.0 per 2.54 cm. , give the yarn a twist in the opposite direction to the first twist (first twist).
これにオーバーコート液を塗布するのが望ましい。It is desirable to apply an overcoat liquid to this.
本発明処理剤を付与した補強mAlで補強すべきゴムの
種類に特に限定はないか、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
ベルト等のゴム製品が得られる。Is there any particular limitation on the type of rubber to be reinforced with reinforcing mAl to which the treatment agent of the present invention has been applied?Hypalon, nitrile rubber,
Hydrogenated nitrile rubber can be used as an example, and very suitable results can be obtained, and rubber products such as timing belts with good heat resistance and durability can be obtained.
[作 用]
ビニルピリジン−スチレン−ブタジエンのターポリマー
ラテックス又はブタジェン系ラテックス、クロロスルフ
ォン化ポリエチレンラテッ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処理液で処理した補強繊
維を用い、又ビニルピリジン−スチレン−ブタジエンの
ターポリマーラテックス又はブタジェン系ラテックス、
クロロスルフォン化ポリエチレンラテックス及びレゾル
シンホルムアルデヒドのを含む第1液で処理した後、加
硫剤、鉛化合物、イソシアネート及びハロゲン含有ポリ
マーを含むオーバーコート液で処理した補強用繊維をゴ
ムの補強に使用することにより、ゴム(マトリクスゴム
)と補強繊維との接着力が、繰返し応力を受けるような
条件下で使用した場合においても、時間の経過とともに
低下するのを防止し、RFL層とオーバーコート層との
界面接着、力を増大させて剥離を防止し、更にイソシア
ネートの使用量を減少させ、イソシアネートを過剰に用
いた場合の屈曲疲労性並びに耐熱性の悪化を防止する。[Function] Using reinforcing fibers treated with a treatment liquid containing a vinylpyridine-styrene-butadiene terpolymer latex or a butadiene-based latex, a chlorosulfonated polyethylene latex, and a water-soluble condensate of resorcinol formaldehyde; Butadiene terpolymer latex or butadiene-based latex,
Use of reinforcing fibers for rubber reinforcement treated with a first liquid containing chlorosulfonated polyethylene latex and resorcin formaldehyde, and then treated with an overcoat liquid containing a vulcanizing agent, a lead compound, an isocyanate, and a halogen-containing polymer. This prevents the adhesive strength between the rubber (matrix rubber) and the reinforcing fibers from decreasing over time even when used under conditions of repeated stress, and improves the bond between the RFL layer and overcoat layer. Interfacial adhesion and force are increased to prevent peeling, and the amount of isocyanate used is reduced to prevent deterioration of bending fatigue properties and heat resistance when excessive isocyanate is used.
又、オーバーコート液自身の経時変化による性能低下を
防止する。It also prevents performance deterioration due to changes in the overcoat liquid itself over time.
[実施例]
ビニルピリジン、スチレン及びブタジェンを15:15
ニア0の割合で含有するビニルピリジン−スチレン−ブ
タジェンのターポリマーラテックス(Pyratex
、商品名、住人ノーガタツタ社製、ターポリマーの含有
量41wt%)65重量部、ブタジェンラテックス(0
700、商品名1日本合成ゴム製、ブタジェンの含有量
57wt%)8重量部、C5Mラテックス(450、商
品名、製鉄化学社製、CSMの含有量40wt%)4重
量部、レゾルシンとホルムアルデヒドの付加縮合物(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。[Example] Vinylpyridine, styrene and butadiene at 15:15
Vinylpyridine-styrene-butadiene terpolymer latex (Pyratex
, trade name, manufactured by Jumanoga Tatsuta Co., Ltd., terpolymer content 41 wt%) 65 parts by weight, butadiene latex (0
700, trade name 1 manufactured by Nippon Synthetic Rubber, butadiene content 57 wt%) 8 parts by weight, C5M latex (450, trade name manufactured by Steel Chemical Co., Ltd., CSM content 40 wt%) 4 parts by weight, addition of resorcin and formaldehyde 15 parts by weight of an aqueous solution containing 20 wt% of condensate (resol), 12 parts by weight of water
parts by weight of the mixture, and 1 part by weight of a mineral oil emulsion (mineral oil content: 55 wt%) as an anti-aging agent.
アンモニア水(濃度18wt%)を1重量部加えて第1
液を得た。Add 1 part by weight of ammonia water (concentration 18 wt%) to the first
I got the liquid.
リサージ0.05重量部、クロロスルフォン化ポリエチ
レン(ハイパロン40、商品名、昭和ネオプレン社製)
6重量部、ポリイソシアネート(MR−200、商品名
、日本ポリウレタン社製) 1.1重量部、p、p’−
ジベンゾイルベンゾキノンジオキシム(加硫剤)1.5
重量部、トルエンを加えて、濃度10wt%のオーバー
コート液を得た。Resurge 0.05 parts by weight, chlorosulfonated polyethylene (Hypalon 40, trade name, manufactured by Showa Neoprene Co., Ltd.)
6 parts by weight, polyisocyanate (MR-200, trade name, manufactured by Nippon Polyurethane Co., Ltd.) 1.1 parts by weight, p, p'-
Dibenzoylbenzoquinone dioxime (vulcanizing agent) 1.5
Parts by weight of toluene were added to obtain an overcoat liquid having a concentration of 10 wt%.
第1液を、9弘のガラス繊維を200本集束してなるガ
ラス繊維束3木を引揃え常法に従って付与した(固型分
17wt%)、250℃で1分間乾燥後、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本引き揃え
て2.54cm当り2.1回のS撚り(上撚り)を施し
たものに第2液を付与した(固型分3%)、これを13
0℃で1分間乾燥したものを、補強繊維として使用し試
験片を作成した。The first liquid was applied to 3 glass fiber bundles made of 200 glass fibers of 9 diameters in a conventional manner (solid content 17 wt%). After drying at 250°C for 1 minute, the glass fiber bundles were 4.0 times of Z twist (pre-twist) per 2.54 cm, and 13 fiber bundles to which this pre-twist has been applied are arranged to give 2.1 times of S twist (pre-twist) per 2.54 cm. A second liquid was applied to the treated material (solid content 3%), and this was
A test piece was prepared by drying it at 0° C. for 1 minute and using it as a reinforcing fiber.
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
ック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。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.
加硫促進剤3重量部、可塑剤5重量部を配合したもの。Contains 3 parts by weight of vulcanization accelerator and 5 parts by weight of plasticizer.
試験片の作成
上記組成を有するゴムを使用し、常法に従いタイミング
ベルトを4未作成した。Preparation of Test Pieces Using rubber having the above composition, four timing belts were prepared according to a conventional method.
このタイミングベルトを使用し、100℃の雰囲気にお
いて600hrベルトの走行テストを実施し、強度低下
を測定した。Using this timing belt, a belt running test was carried out for 600 hours in an atmosphere of 100° C., and the decrease in strength was measured.
上記テスト結果を別表に示す。The above test results are shown in the attached table.
[比較例]
上記実施例の第1液に代え、他の成分の含有量は同一で
あるがCSMを含まない処理液を使用し、同一の実験を
行った結果を別表に示す。[Comparative Example] In place of the first solution in the above example, a treatment solution containing the same contents of other components but not containing CSM was used, and the results of the same experiment are shown in the attached table.
別表 化を使用した場合でも大きな接着力を有する。Separate table It has great adhesion even when used with adhesives.
イソシアネートの使用量を減少させ屈曲疲労性、耐熱性
の悪化を防止できる。By reducing the amount of isocyanate used, it is possible to prevent deterioration of bending fatigue resistance and heat resistance.
オーバーコート液は長期間保存可能であり、第1層とオ
ーバーコート層の間に剥離が生ずることもない。The overcoat liquid can be stored for a long period of time, and no peeling occurs between the first layer and the overcoat layer.
[発明の効果]
本発明処理剤で処理した繊維で補強したゴム製品は耐熱
性が大きく、繰返し屈曲応力を与えても強度が低下せず
、長時間使用に耐えるゴム製品が得られる。[Effects of the Invention] Rubber products reinforced with fibers treated with the treatment agent of the present invention have high heat resistance, do not lose strength even when subjected to repeated bending stress, and can be used for long periods of time.
Claims (2)
リマーラテックス又はブタジエン系ラテックス、クロロ
スルフォン化ポリエチレンラテッ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ゴム補強繊維用処
理液。(1) A treatment liquid for rubber reinforcing fibers containing a terpolymer latex of vinylpyridine-styrene-butadiene or a butadiene-based latex, a chlorosulfonated polyethylene latex, and a water-soluble condensate of resorcin formaldehyde.
リマーラテックス又はブタジエン系ラテックス、クロロ
スルフォン化ポリエチレンラテックス及びレゾルシンホ
ルムアルデヒドのを含む第1液で処理した後、加硫剤、
鉛化合物、イソシアネート及びハロゲン含有ポリマーを
含むオーバーコート液で処理するゴム補強用繊維の処理
方法。(2) After treatment with a first liquid containing a vinylpyridine-styrene-butadiene terpolymer latex or a butadiene-based latex, a chlorosulfonated polyethylene latex, and resorcin formaldehyde, a vulcanizing agent,
A method for treating rubber reinforcing fibers with an overcoat liquid containing a lead compound, an isocyanate, and a halogen-containing polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3605689A JPH02221466A (en) | 1989-02-17 | 1989-02-17 | Treating solution for rubber reinforcing fiber and treatment of rubber reinforcing fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3605689A JPH02221466A (en) | 1989-02-17 | 1989-02-17 | Treating solution for rubber reinforcing fiber and treatment of rubber reinforcing fiber |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23102691A Division JPH05311577A (en) | 1991-08-20 | 1991-08-20 | Treating liquid for fiber for reinforcing rubber |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02221466A true JPH02221466A (en) | 1990-09-04 |
Family
ID=12459061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3605689A Pending JPH02221466A (en) | 1989-02-17 | 1989-02-17 | Treating solution for rubber reinforcing fiber and treatment of rubber reinforcing fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02221466A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135564A (en) * | 1986-11-26 | 1988-06-07 | 日本硝子繊維株式会社 | Glass fiber cord |
-
1989
- 1989-02-17 JP JP3605689A patent/JPH02221466A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135564A (en) * | 1986-11-26 | 1988-06-07 | 日本硝子繊維株式会社 | Glass fiber cord |
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