JP2752744B2 - Treatment agent for fiber for rubber reinforcement - Google Patents
Treatment agent for fiber for rubber reinforcementInfo
- Publication number
- JP2752744B2 JP2752744B2 JP1307238A JP30723889A JP2752744B2 JP 2752744 B2 JP2752744 B2 JP 2752744B2 JP 1307238 A JP1307238 A JP 1307238A JP 30723889 A JP30723889 A JP 30723889A JP 2752744 B2 JP2752744 B2 JP 2752744B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- butadiene
- latex
- styrene copolymer
- copolymer latex
- 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 - Fee Related
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明はゴムベルト、タイヤ等のゴム製品の補強用い
る用にゴム補強用繊維の処理剤に関するものである。さ
らに詳しくは、歯付ベルトの如く、走行中に熱および屈
曲応力の両方を受ける製品の補強剤として使用されるガ
ラス繊維等の処理剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a rubber reinforcing fiber treating agent for reinforcing rubber products such as rubber belts and tires. More specifically, the present invention relates to a treatment agent such as glass fiber used as a reinforcing agent for a product which receives both heat and bending stress during running, such as a toothed belt.
＜従来の技術＞ ゴムベルト、タイヤ等のゴム製品の補強材として、ガ
ラス繊維コード等の補強繊維が広く用いられる。<Related Art> As a reinforcing material for rubber products such as rubber belts and tires, reinforcing fibers such as glass fiber cords are widely used.
ゴムベルト等のゴム製品は繰り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たり、補強繊維が摩耗し、強
度低下が生じ易い。このような屈曲疲労による剥離を防
止し、十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
補強繊維表面に種々の処理剤が塗布される。Rubber products such as rubber belts are repeatedly subjected to bending stress, so that bending fatigue is caused and performance is deteriorated, peeling occurs between a reinforcing material and a rubber matrix, and reinforcing fibers are worn away, and strength is easily reduced. In order to prevent such peeling due to bending fatigue and obtain a sufficient reinforcing effect, it is necessary to increase the affinity between the reinforcing fiber and rubber and the adhesive force, and therefore, various treatment agents are applied to the surface of the reinforcing fiber. Is done.
処理剤としては各種組成のものが提案されている。例
えば特開昭50−3184号公報には、レゾルシン−ホルムア
ルデヒド水溶性縮合物、ビニルピリジン−ブタジエン−
スチレン共重合体ラテックス、カルボキシル化ブタジエ
ン−スチレン共重合体ラテックスおよび非相溶性ワック
ス（例えばパラフィンワックス）を併用した処理剤、ま
た特開昭55−114551号公報には、ビニルピリジン−ブタ
ジエン−スチレン共重合体ラテックス及びレゾルシン−
ホルムアルデヒド水溶性縮合物を併用した処理剤、或は
ブタジエン−スチレンゴム、アクリロニトリル−ブタジ
エンゴム、クロロプレンゴム等の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。Various treatment compositions have been proposed. For example, JP-A-50-3184 discloses a resorcinol-formaldehyde water-soluble condensate, vinylpyridine-butadiene-
A treating agent using a styrene copolymer latex, a carboxylated butadiene-styrene copolymer latex and an incompatible wax (for example, paraffin wax) in combination, and JP-A-55-114551 discloses a vinylpyridine-butadiene-styrene copolymer. Polymer latex and resorcinol
Various treating agents such as a treating agent using a formaldehyde water-soluble condensate in combination, or a treating agent to which a rubber latex such as butadiene-styrene rubber, acrylonitrile-butadiene rubber, and chloroprene rubber is added have been proposed.
＜発明が解決しようとする課題＞ しかしながら、これらの処理剤を用いることにより補
強材とゴムマトリックス間の接着力はある程度満足させ
ることができるが、処理剤自身の耐熱屈曲疲労性が不充
分なため、これらの処理剤で処理した補強繊維を用いた
場合、耐熱耐屈曲疲労性に優れたゴム製品を得難かっ
た。すなわち補強材とゴムマトリックス間の結合力が大
きく、繰り返し屈曲応力を受けても強度が低下せず、あ
るいは補強材とゴムマトリックスとの間の剥離を生ずる
事なく、しかも充分な耐熱性を有する処理剤は従来知ら
れていない。<Problems to be Solved by the Invention> However, by using these treatment agents, the adhesive force between the reinforcing material and the rubber matrix can be satisfied to some extent, but since the heat resistance of the treatment agents themselves is insufficient due to the heat bending fatigue resistance. When the reinforcing fibers treated with these treating agents were used, it was difficult to obtain a rubber product excellent in heat resistance and bending fatigue resistance. That is, the bonding strength between the reinforcing material and the rubber matrix is large, and the strength does not decrease even when subjected to repeated bending stress, or the peeling between the reinforcing material and the rubber matrix does not occur, and the process has sufficient heat resistance. Agents have not been previously known.
近年、自動車エンジン付近の温度上昇にともないタイ
ミングベルトの補強材として使用された場合、優れた耐
熱耐屈曲疲労性はさらに必要であり、工業的に満足すべ
き処理剤は知られていなかった。In recent years, when used as a reinforcing material for a timing belt with a rise in temperature near an automobile engine, excellent heat resistance and bending fatigue resistance are further required, and no industrially satisfactory treating agent has been known.
本発明の目的は、従来技術の有していた前述の欠点を
解消することにある。An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art.
＜課題を解決するための手段＞ 本発明は前述の欠点を解決する目的のもとになされた
ものであり、レゾルシン−ホルムアルデヒド水溶性縮合
物（Ａ）、カルボキシル化ビニルピリジン−ブタジエン
−スチレン共重合体ラテックス（Ｂ）及び上記（Ｂ）を
除くゴムラテックス（Ｃ）を含み、且つこれらの
（Ａ），（Ｂ），（Ｃ）成分の割合が固形分比率で各々
２〜15wt％、15〜80wt％、15〜70wt％であることを特徴
とするゴム補強用繊維の処理剤にある。次に、本発明を
更に具体的に説明する。<Means for Solving the Problems> The present invention has been made with the object of solving the above-mentioned drawbacks, and includes resorcinol-formaldehyde water-soluble condensate (A), carboxylated vinylpyridine-butadiene-styrene copolymer. It contains the combined latex (B) and the rubber latex (C) excluding the above (B), and the proportions of the components (A), (B) and (C) are 2 to 15 wt% and 15 to 15 wt%, respectively, in terms of solid content. A rubber reinforcing fiber treating agent characterized in that the amount is 80 wt% and 15 to 70 wt%. Next, the present invention will be described more specifically.
本発明における（Ａ）成分であるレゾルシン−ホルム
アルデヒド水溶性縮合物（以下RF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
ール型の水溶性付加縮合物が好適に使用できる。特に好
ましくはレゾルシンとホルムアルデヒドの反応モル比が
1:0.5〜３の割合で反応させたものが望ましい。As the resorcinol-formaldehyde water-soluble condensate (hereinafter referred to as RF) as the component (A) in the present invention, a resorcin-type water-soluble condensate obtained by reacting resorcinol and formaldehyde in the presence of an alkali catalyst such as an alkali hydroxide or an amine. Addition condensates can be suitably used. Particularly preferably, the reaction molar ratio of resorcinol to formaldehyde is
It is desirable to react at a ratio of 1: 0.5-3.
また（Ｂ）成分であるカルボキシル化ビニルピリジン
−ブタンジエン−スチレン共重合体ラテックスとして
は，重合成分比率でエチレン性不飽和ジカルボン酸１〜
10wt％、ビニルピリジン10〜20wt％、ブタジェン10〜30
wt％およびスチレン60〜75wt％の共重合体を含有するも
のが有利に用いられる。代表的なカルボキシル化ビニル
ピリジン−ブタジエン−スチレン共重合体ラテックスと
して、NIPOGUARD Z−500（商品名、日本ゼオン製）が好
適に使用できる。As the carboxylated vinylpyridine-butanediene-styrene copolymer latex as the component (B), the proportion of the ethylenically unsaturated dicarboxylic acid 1 to polymerization component is 1
10wt%, vinylpyridine 10-20wt%, butadiene 10-30
Those containing copolymers by weight of 60% and 75% by weight of styrene are advantageously used. As a typical carboxylated vinylpyridine-butadiene-styrene copolymer latex, NIPOGUARD Z-500 (trade name, manufactured by Zeon Corporation) can be suitably used.
（Ｃ）成分のゴムラテックスとしてはブタジエン−ス
チレン共重合体ラテックス、ジカルボキシル化ブタジエ
ン−スチレン共重合体ラテックス、クロロスルホン化ポ
リエチレンラテックス等を好適に使用できる。これらの
中でジカルボキシル化ブタジエン−スチレン共重合体ラ
テックス、或は（および）クロロスルホン化ポリエチレ
ンラテックスを使用した場合特に好適な結果を得ること
が出来る。As the rubber latex of the component (C), butadiene-styrene copolymer latex, dicarboxylated butadiene-styrene copolymer latex, chlorosulfonated polyethylene latex, and the like can be suitably used. Among these, particularly preferred results can be obtained when dicarboxylated butadiene-styrene copolymer latex or (and) chlorosulfonated polyethylene latex is used.
ジカルボキシル化ブタジエン−スチレン共重合体ラテ
ックスとしては、重合成分比率でブタジエン20〜80wt
％、スチレン５〜70wt％およびエチレン性不飽和ジカル
ボン酸１〜10wt％を含有するものが特に適当であり、Ni
pol 2570X5（商品名、日本ゼオン製）、JSR 0668（商品
名、日本合成ゴム製）等が好適に使用できる。ブタジエ
ン−スチレン共重合体ラテックスとしては、Niopl LX 1
10（商品名、日本ゼオン製）、J9040（商品名、住友ノ
ーガタック製）等が、またクロロスルホン化ポリエチレ
ンラテックスとしては、塩素含量25〜43wt％および硫黄
含量1.0〜1.5wt％のクロロスルホン化ポリエチレンのラ
テックスが有利に用いられる。代表的なクロロスルホン
化ポリエチレンラテックスとして、Esprene 200（商品
名、住友化学製）等が好適に使用できる。As a dicarboxylated butadiene-styrene copolymer latex, butadiene 20 to 80 wt.
%, 5 to 70% by weight of styrene and 1 to 10% by weight of ethylenically unsaturated dicarboxylic acid are particularly suitable.
Pol 2570X5 (trade name, manufactured by Zeon Corporation), JSR 0668 (trade name, manufactured by Japan Synthetic Rubber) and the like can be suitably used. Butadiene-styrene copolymer latex is Niopl LX 1
10 (trade name, manufactured by Zeon Corporation), J9040 (trade name, manufactured by Sumitomo Nogatac) and the like, and as the chlorosulfonated polyethylene latex, chlorosulfonated with a chlorine content of 25 to 43 wt% and a sulfur content of 1.0 to 1.5 wt% A latex of polyethylene is advantageously used. As a typical chlorosulfonated polyethylene latex, Esprene 200 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) or the like can be suitably used.
本発明においてはレゾルシン−ホルムアルデヒド水溶
性縮合物、カルボキシル化ビニルピリジン−ブタジエン
−スチレン共重合体ラテックス及びその他のゴムラテッ
クスの割合を固形分比率として各々２〜15wt％、15〜80
wt％、15〜70wt％として三者を均一に混合する。In the present invention, the proportions of the resorcinol-formaldehyde water-soluble condensate, carboxylated vinylpyridine-butadiene-styrene copolymer latex and other rubber latex are defined as solid content ratios of 2 to 15% by weight and 15 to 80%, respectively.
wt%, 15-70wt%, and uniformly mix the three.
このようにして得られた本発明処理剤中のカルボキシ
ル化ビニルピリジン−ブタジエン−スチレン共重合体ラ
テックスの割合が上記範囲より小さい場合は、得られる
耐熱耐屈曲疲労性が充分ではなく、又割合があまり大き
いと本発明処理剤の被膜が硬く成りすぎ、必要とする被
膜の柔軟性が得られず、本発明の効果が期待できない。When the ratio of the carboxylated vinylpyridine-butadiene-styrene copolymer latex in the thus-obtained treating agent of the present invention is smaller than the above range, the obtained heat-resistant bending fatigue resistance is not sufficient, and the ratio is low. If it is too large, the coating of the treatment agent of the present invention becomes too hard, the required flexibility of the coating cannot be obtained, and the effects of the present invention cannot be expected.
RFの割合があまり大きいと、本発明処理剤の被膜が硬
くなり、充分な耐屈曲疲労性が得られない。又この割合
が小さすぎるとゴムマトリックスとの接着力が低下し易
い。If the ratio of RF is too large, the coating of the treating agent of the present invention becomes hard, and sufficient bending fatigue resistance cannot be obtained. If the ratio is too small, the adhesive strength to the rubber matrix tends to decrease.
本発明の処理剤の固形分濃度は10〜40wt％、好ましく
は20〜30wt％とするのが適当である。濃度があまり低い
と補強繊維への付着が不充分となり、又濃度が高すぎる
と補強繊維への付着量のコントロールが難しくなり、均
一な付着量の補強繊維が得難い。The solid concentration of the treating agent of the present invention is suitably from 10 to 40% by weight, preferably from 20 to 30% by weight. If the concentration is too low, adhesion to the reinforcing fibers will be insufficient, and if the concentration is too high, it will be difficult to control the amount of adhesion to the reinforcing fibers, and it will be difficult to obtain a reinforcing fiber with a uniform amount of adhesion.
好ましいゴム補強用繊維の処理剤の一例はレゾルシン
−ホルムアルデヒド水溶液性縮合物、カルボキシル化ビ
ニルピリジン−ブタジエン−スチレン共重合体ラテック
ス、ジカルボキシル化ブタジエン−スチレン共重合体ラ
テックス、及びクロロスルホン化ポリエチレンラテック
スを含み、且つこれらの割合が固形分比率で各々２〜15
wt％、15〜80wt％、７〜50wt％、10〜60wt％である。Examples of preferred rubber reinforcing fiber treating agents include resorcinol-formaldehyde aqueous condensate, carboxylated vinylpyridine-butadiene-styrene copolymer latex, dicarboxylated butadiene-styrene copolymer latex, and chlorosulfonated polyethylene latex. And these ratios are 2 to 15
wt%, 15-80 wt%, 7-50 wt%, 10-60 wt%.
本発明の処理剤は前述したRF、カルボキシル化ビニル
ピリジン−ブタジエン−スチレン共重合体ラテックス、
およびその他のゴムラテックスを必須成分とするが必要
に応じ、pHを調整するため塩基、例えばアンモニアを含
有することができ、さらに安定剤、老化防止剤等を含有
することが出来る。The treating agent of the present invention is the aforementioned RF, carboxylated vinylpyridine-butadiene-styrene copolymer latex,
And other rubber latex as an essential component, but if necessary, may contain a base such as ammonia for adjusting pH, and may further contain a stabilizer, an antioxidant and the like.
本発明処理剤を塗布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付与して200本程度集束
したガラス繊維束を３本引き揃え、これに常法に従い、
本発明処理剤を塗布、乾燥し、これに2.54cm（１イン
チ）当り0.5〜4.0回程度のＳ、又はＺ撚り（下撚り）を
施したものを、更に２〜13本程度合糸して2.54cm当り1.
0〜4.5回程度のＺ、又はＳ撚り（上撚り）を施したコー
ドが好適に使用できる。なお補強繊維に対する処理剤の
塗布量は固形分として10〜30wt％程度とするのが適当で
ある。Although there is no particular limitation on the reinforcing fibers to which the treatment agent of the present invention is applied, it is practical to use glass fibers. For example, a sizing agent is applied to a glass fiber having a thickness of 9μ, and three glass fiber bundles bundled about 200 are aligned.
The treatment agent of the present invention is applied, dried, and subjected to S- or Z-twisting (primary twisting) of about 0.5 to 4.0 times per 2.54 cm (1 inch). 2.54cm 1.
A cord that has been subjected to about 0 to 4.5 times of Z or S twist (twisting) can be suitably used. The amount of the treatment agent applied to the reinforcing fibers is suitably about 10 to 30% by weight as a solid content.
本発明処理剤を施され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、クロロプレンゴム、アクリロ
ニトリルブタジエンゴム、クロロスルホン化ポリエチレ
ンゴム、等が例示でき、極めて好適な結果を得ることが
出来る。There is no particular limitation on the type of rubber to be reinforced with the reinforcing fibers provided with the treatment agent of the present invention, but chloroprene rubber, acrylonitrile butadiene rubber, chlorosulfonated polyethylene rubber, and the like can be exemplified, and extremely favorable results can be obtained. I can do it.
＜作用＞ 本発明処理剤はカルボキシル化ビニルピリジン−ブタ
ジエン−スチレン共重合体ラテックスを含有しているの
で、カルボキシル基とピリジル基とが水素結合によるポ
リマーネットワークを形成することによって、ポリマー
の架橋構造が緻密になり、本発明処理剤の被膜強度がよ
り強靱になることから、本発明処理剤で処理した補強繊
維同志あるいは補強繊維とゴムマトリックス間に減摩作
用が生じ、繊維の摩耗が防止されるとともに、応力が緩
和され、繰り返し屈曲応力を受けた場合疲労が生じ難く
なるものと思われる。<Action> Since the treating agent of the present invention contains a carboxylated vinylpyridine-butadiene-styrene copolymer latex, a carboxyl group and a pyridyl group form a polymer network by hydrogen bonding, whereby a crosslinked structure of the polymer is formed. Since the coating becomes denser and the coating strength of the treating agent of the present invention becomes more tough, a friction-reducing effect occurs between the reinforcing fibers treated with the treating agent of the present invention or between the reinforcing fibers and the rubber matrix, thereby preventing abrasion of the fibers. At the same time, the stress is relieved, and it is considered that fatigue is less likely to occur when repeatedly subjected to bending stress.
以下実施例により本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail by way of examples.
＜実施例＞ 実施例１ （１）直径９μｍの無アルカリガラスのフィラメントを
紡糸し、これを集束剤により集束して33.7テックスのガ
ラスストランドを得、これを３本合糸させ下記組成、 レゾルシン−ホルムアルデヒド水溶液性縮合物 （固形分含量8wt％） 30重量部 カルボキシル化ビニルピリジン−ブタジエン−スチレン
共重合体ラテックス（Nipoguard Z−500固形分含量40wt
％） 45重量部 ジカルボキシル化ブタジエン−スチレン共重合体ラテッ
クス（JSR 0650固形含量40wt％） 20重量部 25％アンモニア水 １重量部 水 ４重量部 からなる処理剤を常法に従ってガラス繊維束に対し固
形分が約20wt％となるよう付与した。次にこのガラス繊
維束を１インチ当り2.1回のＺ方向（Ｓ方向）の下撚り
を与え更にこの下撚りを与えた繊維束を13本合糸して１
インチ当り2.1回のＳ方向（Ｚ方向）の上撚りを施し、E
CG150 3/13 2.1S（Ｚ）のガラス繊維コードを得た。こ
のコード補強繊維として以下のような試験片および巾19
mm、長さ880mmの歯付きベルトを作成した。<Examples> Example 1 (1) A filament of non-alkali glass having a diameter of 9 µm was spun and bundled with a sizing agent to obtain a glass strand of 33.7 tex. Formaldehyde aqueous condensate (solid content 8 wt%) 30 parts by weight Carboxylated vinylpyridine-butadiene-styrene copolymer latex (Nipoguard Z-500 solids content 40 wt
%) 45 parts by weight Dicarboxylated butadiene-styrene copolymer latex (JSR 0650 solid content 40 wt%) 20 parts by weight 25% 1% aqueous ammonia 4 parts by weight water It was applied so that the solid content was about 20% by weight. Next, the glass fiber bundle is subjected to 2.1 times of twisting in the Z direction (S direction) per inch, and 13 fiber bundles to which the twisting has been performed are combined to obtain 1 fiber.
2.1 twists in the S direction (Z direction) per inch
CG150 3/13 A glass fiber cord of 2.1S (Z) was obtained. The following test piece and width 19 are used as this cord reinforcing fiber.
mm, a 880 mm long toothed belt was prepared.
このコードを長さ120mmの長さに切断し、表−１の配
合の未加硫クロロプレンゴムシートの上に20本平行に並
べ（全幅25mm）、これを上下方向から,150℃で25分間、
プレスして加硫した。加硫後、コードの尖端部とゴムの
尖端 部とを強固に把握し、互いに反対方向に引っ張って、コ
ードをゴムから引き剥して接着性を調べ、次の基準によ
って判定した。This cord is cut to a length of 120 mm, and 20 cords are arranged in parallel on an unvulcanized chloroprene rubber sheet having the composition shown in Table 1 (total width: 25 mm).
Pressed and vulcanized. After vulcanization, the tip of the cord and the tip of the rubber The part was firmly grasped, pulled in the opposite direction, the cord was peeled off from the rubber, and the adhesion was examined.
◎；ゴム破壊、○;3/4以上ゴム破壊、 △;1/2以上ゴム破壊、×；ゴム破壊せず、 接着力は、◎が最大で、順次○、△および×の順に低
下する。◎: rubber fracture,;: rubber fracture of 3/4 or more, Δ; rubber fracture of 1/2 or more, ×: no rubber fracture, the adhesive force is maximum at ◎, and decreases sequentially in the order of △, △ and ×.
また歯付きベルトを6000rpmの駆動モーターを備えた
走行試験機に装着し、80℃の雰囲気中で1000時間走行さ
せた後の引張り強度保持率を求めた。Further, the toothed belt was attached to a running test machine equipped with a drive motor of 6000 rpm, and the tensile strength retention after running for 1000 hours in an atmosphere of 80 ° C. was determined.
又室温で上記組成処理剤の被膜を作成し、250℃で２
分間熱処理を施した後、150℃で25分間プレスして厚さ1
mmのシートを得た。Also, form a film of the above composition at room temperature,
Heat treatment at 150 ° C for 25 minutes
mm sheet was obtained.
このシートを巾10mmに裁断して短冊状の試験片を得
た。この試験片についてMIT試験機を使用して試料片が
切断するまでの屈曲回数を求めた。これら測定結果を表
−２に示す。This sheet was cut into a width of 10 mm to obtain a strip-shaped test piece. Using the MIT tester, the number of flexures before the test piece was cut was determined for this test piece. Table 2 shows the measurement results.
比較例１ カルボキシル化ビニルピリジン−ブタジエン−スチレ
ン共重合体ラテックスの替わりにビニルピリジン−ブタ
ジエン−スチレン共重合体ラテックス（Nipol 2518FS固
形分含量40wt％ 日本ゼオン製）を用いる他は全く実施
例１と同様な試験を行なった結果を表−２に示す。Comparative Example 1 Same as Example 1 except that a vinylpyridine-butadiene-styrene copolymer latex (Nipol 2518FS solid content: 40 wt%, manufactured by Zeon Corporation) was used instead of the carboxylated vinylpyridine-butadiene-styrene copolymer latex. Table 2 shows the results of the various tests.
実施例２ レゾルシン−ホルムアルデヒド水溶液性縮合物 （固形分含量8wt％） 30重量部 カルボキシル化ビニルピリジン−ブタジエン−スチレン
共重合体ラテックス（Nipoguard Z−500固形分含量40wt
％） 30重量部 ジカルボキシル化ブタジエン−スチレン共重合体ラテッ
クス（JSR 0650固形分含量40wt％） 15重量部 クロロスルホン化ポリエチレンラテックス（Esprene 20
0 固形分含量40wt％） 20重量部 25％アンモニア水 １重量部 水 ４重量部 から成る処理剤を用いて、実施例１と同様な試験を行
なった結果を表−２に示す。Example 2 Resorcin-formaldehyde aqueous solution condensate (solid content 8 wt%) 30 parts by weight Carboxylated vinylpyridine-butadiene-styrene copolymer latex (Nipoguard Z-500 solid content 40 wt.
%) 30 parts by weight Dicarboxylated butadiene-styrene copolymer latex (JSR 0650 solid content 40 wt%) 15 parts by weight chlorosulfonated polyethylene latex (Esprene 20)
0 solid content: 40 wt%) A test was conducted in the same manner as in Example 1 using a treating agent consisting of 20 parts by weight, 25% aqueous ammonia, 1 part by weight, and water, 4 parts by weight. Table 2 shows the results.
比較例２ カルボキシル化ビニルピリジン−ブタジエン−スチレ
ン共重合体ラテックスの替わりにビニルピリジン−ブタ
ジエン−スチレン共重合体ラテックス（Nipol 2518FS
固形分含量40wt％ 日本ゼオン製）を用いる他は全く実
施例２と同様な試験を行なった結果を表−２に示す。Comparative Example 2 A vinylpyridine-butadiene-styrene copolymer latex (Nipol 2518FS) was used instead of the carboxylated vinylpyridine-butadiene-styrene copolymer latex.
Except for using a solid content of 40 wt% (manufactured by Zeon Corporation), the same test as in Example 2 was conducted, but the results are shown in Table 2.
＜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、繰り返し屈曲応力を与えても強度が低下
せず、補強繊維の摩耗が生じ難い。<Effect of the Invention> A rubber product reinforced with the fiber treated with the treating agent of the present invention has high heat resistance, does not decrease in strength even when repeatedly subjected to bending stress, and hardly causes abrasion of the reinforcing fiber.
Claims (4)
物（Ａ）、カルボキシル化ビニルピリジン−スチレン−
ブタジエン共重合体ラテックス（Ｂ）及び上記（Ｂ）成
分を除くゴムラテックス（Ｃ）を含み、且つこれら
（Ａ），（Ｂ），（Ｃ）成分の割合が固形分比率で各々
２〜15wt％、15〜80wt％、15〜70wt％であることを特徴
とするゴム補強用繊維の処理剤。1. A resorcinol-formaldehyde water-soluble condensate (A), a carboxylated vinylpyridine-styrene-
It contains a butadiene copolymer latex (B) and a rubber latex (C) excluding the above-mentioned component (B), and the ratio of each of these components (A), (B) and (C) is 2 to 15% by weight in terms of solid content. , 15 to 80 wt%, 15 to 70 wt%.
スチレン共重合体ラテックス、ジカルボキシル化ブタジ
エン−スチレン共重合体ラテックス、及びクロロスルホ
ン化ポリエチレンラテックスからなる群より選ばれた少
なくとも１種である特許請求の範囲第１項記載のゴム補
強用繊維の処理剤。2. The rubber latex (C) comprises butadiene-
2. The treatment of the rubber reinforcing fiber according to claim 1, which is at least one selected from the group consisting of a styrene copolymer latex, a dicarboxylated butadiene-styrene copolymer latex, and a chlorosulfonated polyethylene latex. Agent.
合物、カルボキシル化ビニルピリジン−ブタジエン−ス
チレン共重合体ラテックス、ジカルボキシル化ブタジエ
ン−スチレン共重合体ラテックス、及びクロロスルホン
化ポリエチレンラテックスを含み、且つこれらの割合が
固形分比率で各々２〜15wt％、15〜80wt％、７〜50wt
％、10〜60wt％であることを特徴とするゴム補強用繊維
の処理剤。3. An aqueous condensate of a resorcinol-formaldehyde aqueous solution, a carboxylated vinylpyridine-butadiene-styrene copolymer latex, a dicarboxylated butadiene-styrene copolymer latex, and a chlorosulfonated polyethylene latex. Is 2 to 15 wt%, 15 to 80 wt%, 7 to 50 wt%
%, 10 to 60% by weight.
用繊維の処理剤を補強繊維に対して固形分として10〜30
重量％付着させたゴム補強用繊維。4. The treatment agent for rubber reinforcing fibers according to claim 1, wherein the treating agent for the reinforcing fibers is 10 to 30 as a solid content relative to the reinforcing fibers.
Rubber reinforcing fiber with weight% attached.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307238A JP2752744B2 (en) | 1989-11-27 | 1989-11-27 | Treatment agent for fiber for rubber reinforcement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307238A JP2752744B2 (en) | 1989-11-27 | 1989-11-27 | Treatment agent for fiber for rubber reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03167376A JPH03167376A (en) | 1991-07-19 |
| JP2752744B2 true JP2752744B2 (en) | 1998-05-18 |
Family
ID=17966700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1307238A Expired - Fee Related JP2752744B2 (en) | 1989-11-27 | 1989-11-27 | Treatment agent for fiber for rubber reinforcement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2752744B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107904950A (en) * | 2017-12-14 | 2018-04-13 | 芜湖华烨新材料有限公司 | A kind of industrial cloth anti-corrosion dipping solution |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0450144A (en) * | 1990-06-18 | 1992-02-19 | Asahi Fiber Glass Co Ltd | Rubber-reinforcing fiber |
| WO1994012443A1 (en) * | 1992-12-01 | 1994-06-09 | Nippon Glass Fiber Co., Ltd. | Glass fiber for rubber reinforcement |
| JP2005009010A (en) * | 2003-06-18 | 2005-01-13 | Asahi Fiber Glass Co Ltd | Reinforcing fiber for rubber product |
| JP2012067410A (en) * | 2010-09-24 | 2012-04-05 | Central Glass Co Ltd | Coating liquid for coating glass fiber and glass fiber for reinforcing rubber using the same |
| CN104141232A (en) * | 2014-07-24 | 2014-11-12 | 旌德县合力工业布厂 | Anti-corrosion dipping liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02167346A (en) * | 1988-12-21 | 1990-06-27 | Yokohama Rubber Co Ltd:The | Bonding treatment between ethylene propylene-based copolymer rubber composition and aliphatic polyamide fiber |
-
1989
- 1989-11-27 JP JP1307238A patent/JP2752744B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02167346A (en) * | 1988-12-21 | 1990-06-27 | Yokohama Rubber Co Ltd:The | Bonding treatment between ethylene propylene-based copolymer rubber composition and aliphatic polyamide fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107904950A (en) * | 2017-12-14 | 2018-04-13 | 芜湖华烨新材料有限公司 | A kind of industrial cloth anti-corrosion dipping solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03167376A (en) | 1991-07-19 |
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