JPH01284532A - Coating agent for glass fiber cord for reinforcing rubber - Google Patents
Coating agent for glass fiber cord for reinforcing rubberInfo
- Publication number
- JPH01284532A JPH01284532A JP11413588A JP11413588A JPH01284532A JP H01284532 A JPH01284532 A JP H01284532A JP 11413588 A JP11413588 A JP 11413588A JP 11413588 A JP11413588 A JP 11413588A JP H01284532 A JPH01284532 A JP H01284532A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- rubber
- latex
- fiber cord
- resorcinol
- 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
- 239000003365 glass fiber Substances 0.000 title claims abstract description 42
- 229920001971 elastomer Polymers 0.000 title claims abstract description 25
- 239000005060 rubber Substances 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 230000003014 reinforcing effect Effects 0.000 title abstract description 4
- 229920000126 latex Polymers 0.000 claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 229920005610 lignin Polymers 0.000 claims abstract description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002787 reinforcement Effects 0.000 claims description 9
- 239000004816 latex Substances 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000376 effect on fatigue Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はゴム補強用硝子繊維コード被覆剤に関し、更に
詳しくは耐）ノー耐老化性及び１ｌｊ（屈曲疲労性が優
れたゴム補強用硝子繊維を与えるゴム補強用硝子繊維コ
ート被覆剤に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a glass fiber cord coating material for rubber reinforcement, and more specifically, a glass fiber cord coating material for rubber reinforcement that has excellent no-aging resistance and 1lj (flexural fatigue resistance). This invention relates to a glass fiber coating material for rubber reinforcement.
〔従来の技術及び発明が解決しようとする課題〕ガラス
繊維は引張り強度が高く、高モジュラスを有し、繰返し
伸長に対してほぼ弾性変形を示し、特に高モジュラスの
ため一般のゴム補強用有機繊維に比して温度依存性が小
さく、また水分、熱に対する寸法安定性が良好であるな
どの特性を有する。これらの特性は、タイヤ、ベルト、
ホースなどのゴム製品の補強用材料として特に好ましい
ものである。[Prior art and problems to be solved by the invention] Glass fiber has high tensile strength and high modulus, and exhibits almost elastic deformation when stretched repeatedly. It has characteristics such as less temperature dependence than that of other materials, and good dimensional stability against moisture and heat. These characteristics apply to tires, belts,
It is particularly preferred as a reinforcing material for rubber products such as hoses.
しかるにガラス繊維の重大な欠点の１つはフィラメント
間の相互摩擦が非常に弱く、ゴム補強用材料に要求され
る重要な特性である耐疲労性に劣ることであり、さらに
もう１つの欠点はガラス繊維自体はゴムとの接着性を存
しないことである。However, one of the major drawbacks of glass fiber is that the mutual friction between the filaments is very weak, resulting in inferior fatigue resistance, which is an important property required for rubber reinforcing materials. The fiber itself has no adhesive property with rubber.
従ってガラス繊維の接着剤処理は、ガラス繊維にゴムと
の接着性を与えると同時にガラス繊維の面］疲労性を改
良するものでなりればならない。この点にレイヨン、ナ
イロン、ポリエステルの如き有機繊維からなるゴム補強
用材料の接着剤処理とは根本的な相違がある。Therefore, the treatment of glass fibers with an adhesive must give the glass fibers adhesion to rubber and at the same time improve the surface fatigue properties of the glass fibers. In this respect, there is a fundamental difference from the adhesive treatment of rubber reinforcing materials made of organic fibers such as rayon, nylon, and polyester.
即ち、有機繊維からなるゴム補強用材料の接着剤処理に
おいては、接着剤（一般的にレゾルシンホルマリン樹脂
ラテンクスが使用される）をたかだかコード表面のフィ
ラメンＩ・から内層へ２〜３層に浸透せしめるのみで接
着効果は充分であって、コード内部まで完全に接着剤で
充満させる必要はなく、むしろ深層までの浸透は耐疲労
性に悪影響がある。従って接着剤のコードに対する付着
量も１０％以下で充分である。That is, in the adhesive treatment of rubber reinforcing materials made of organic fibers, the adhesive (generally resorcin formalin resin Latinx is used) is infiltrated into at most 2 to 3 layers from the filament I on the surface of the cord to the inner layer. The adhesive effect is sufficient just by using adhesive alone, and it is not necessary to completely fill the inside of the cord with adhesive; rather, penetration into deep layers has a negative effect on fatigue resistance. Therefore, it is sufficient that the amount of adhesive attached to the cord is 10% or less.
これに対してガラス繊維の接着剤処理においては、接着
剤（−船釣にレゾルソンホルマリン樹脂ラテックスが使
用される）がコード内層フィラメント間にまで浸透し、
コードを構成する各フィラメントを完全に接着剤で包含
し、フィラメント相互の摩擦を防止する必要がある。そ
のため必然的に接着剤の付着量も１５〜２５％と有機繊
維に比して著しく多くなる。この様に各フィラメントを
完全に接着剤で包含することにより以下の問題が発生す
る。即ち該コードを使用した成形物が熱環境下におかれ
た場合、接着剤の熱老化が急速に進み、それによって接
着剤自身の柔軟性の低下をきたし、ひいては成形物の屈
曲によって接着剤層の破壊をまねく。このことによって
接着剤の重要な機能であるガラス繊維とゴムとの接着性
及びガラス繊維フィラメント相互の摩擦を防止する機能
の低下をきたす。従って該コードをタイヤ、ベルト、ホ
ース等のゴム補強用材料として使用した場合寿命の低下
原因となる。On the other hand, when glass fibers are treated with adhesive, the adhesive (Resolson formalin resin latex is used for boat fishing) penetrates between the inner filaments of the cord.
It is necessary to completely enclose each filament making up the cord with adhesive to prevent friction between the filaments. Therefore, the amount of adhesive attached is necessarily 15 to 25%, which is significantly larger than that of organic fibers. Completely covering each filament with adhesive in this manner causes the following problems. That is, when a molded product using the cord is placed in a thermal environment, the adhesive rapidly ages due to heat, which causes a decrease in the flexibility of the adhesive itself, and the bending of the molded product causes the adhesive layer to deteriorate. leading to the destruction of This causes a decline in the adhesive's important functions of adhesion between glass fibers and rubber and the ability to prevent friction between glass fiber filaments. Therefore, when the cord is used as a rubber reinforcing material for tires, belts, hoses, etc., it causes a reduction in the lifespan.
今日、自動車エンジンルームの温度上昇に伴い、レゾル
シン・ホルムアルデヒド樹脂ラテックスで処理した硝子
繊維コードを用いたタイミングベルトは、熱によりラテ
ックスの老化が急速に進み、ヘルド寿命を短くする欠点
があった。すなわち、レゾルシン・ホルムアルデヒド樹
脂ラテックス中のラテックスが熱により老化しもろくな
り、硝子繊維の保護及び７トリソクスゴムとの接着性の
低下をきたすことによって、硝子繊維コードかヘルドの
芯線としての機能低下をきたし、結局、これが進行する
とベルトの切断となっていた。Today, with the rise in temperature in automobile engine compartments, timing belts that use glass fiber cords treated with resorcinol-formaldehyde resin latex have the disadvantage that the latex ages rapidly due to heat, shortening the belt's lifespan. In other words, the latex in the resorcinol-formaldehyde resin latex ages and becomes brittle due to heat, which reduces the protection of the glass fibers and the adhesion to the 7-trisox rubber, resulting in a decline in the functionality of the glass fiber cord as a core wire for the heald. Eventually, as this progressed, the belt would break.
本発明の目的は、上記した不都合の解消にあり、耐熱耐
老化性及び耐屈曲疲労性が優れたゴム補強用硝子繊維を
与えるゴム補強用硝子ｔ＆維コード被覆剤を提供するこ
とにある。An object of the present invention is to eliminate the above-mentioned disadvantages, and to provide a rubber reinforcing glass t-shirt and fiber cord coating material that provides rubber reinforcing glass fibers with excellent heat resistance, aging resistance, and bending fatigue resistance.
本発明のゴム補強用硝子繊維コード被覆剤は、レゾルシ
ン・ホルムアルデヒド樹脂ゴムラテックスとリグニンか
らなることを特徴とするものである。The rubber-reinforcing glass fiber cord coating material of the present invention is characterized by comprising a resorcinol-formaldehyde resin rubber latex and lignin.
本発明に使用されるレゾルシン・ホルムアルデヒド樹脂
ゴムラテックスのラテックスとしては、例えば、天然ゴ
ムラテックス、スチレン・ブタジェン共重合ラテックス
、スチレン・ブタジェン・ビニルピリジン共重合ラテッ
クス、アクリロニトリル・ブタジェン共重合ラテックス
、クロロプレンラテンクス、ネオブレンラテンクス、ブ
チルゴムラテックス等の合成ゴムラテックス；カルボキ
シル化スチレン・ブタジェンラテックス、カルボキシル
化アクリロニトリル・ブタジェンラテックス等の変性ラ
テックス等の１種、またはこれらの２種以上の混合物を
挙げることができる。Examples of the resorcinol-formaldehyde resin rubber latex used in the present invention include natural rubber latex, styrene-butadiene copolymer latex, styrene-butadiene-vinylpyridine copolymer latex, acrylonitrile-butadiene copolymer latex, and chloroprene latex. Synthetic rubber latex such as , neorene latex, butyl rubber latex; modified latex such as carboxylated styrene/butadiene latex, carboxylated acrylonitrile/butadiene latex, etc., or a mixture of two or more of these may be mentioned. can.
本発明に使用されるリグニンは老化防止剤として添加さ
れるべきものであって、これによって硝子繊維コードの
耐屈曲疲労性を改善する。このリグニンを老化防止剤と
して用いる利点は、一般に知られた老化防止剤が水溶性
でないためレゾルシン・ホルムアルデヒド樹脂ゴムラテ
ックス中で分散させる必要があるのに対し、このリグニ
ンは水溶性であるためその作業が極めて簡易であり、し
かも一般の老化防止剤と比較して安価に入手できる点に
ある。The lignin used in the present invention is to be added as an anti-aging agent, thereby improving the flex fatigue resistance of the glass fiber cord. The advantage of using this lignin as an anti-aging agent is that generally known anti-aging agents are not water-soluble and must be dispersed in resorcinol formaldehyde resin rubber latex, whereas this lignin is water-soluble and cannot be easily dispersed. It is extremely simple and can be obtained at a lower cost than general anti-aging agents.
このリグニンのゴム補強用硝子繊維コード被覆剤におけ
る添加割合はラテックスの固形分比で、通常、０．５〜
５．０％である。この添加割合が０．５％未満では、老
化防止効果が小さく、５．０％を超えるとガラス繊維と
ゴムとの接着性の低下原因となり望ましくない。好まし
くは、１．０〜３．０％である。The addition ratio of this lignin to the glass fiber cord coating material for rubber reinforcement is the solid content ratio of the latex, and is usually 0.5 to 0.5.
It is 5.0%. If the addition ratio is less than 0.5%, the anti-aging effect will be small, and if it exceeds 5.0%, it will cause a decrease in the adhesion between glass fiber and rubber, which is not desirable. Preferably it is 1.0 to 3.0%.
本発明のゴム補強用硝子繊維コード被覆剤は、前記した
レゾルシン・ホルムアルデヒド樹脂ゴムラテックスの水
溶液中に上記したリグニンを添加混合して容易に製造さ
れる。The rubber-reinforcing glass fiber cord coating material of the present invention is easily produced by adding and mixing the above-described lignin into an aqueous solution of the above-described resorcinol-formaldehyde resin rubber latex.
本発明のゴム補強用硝子繊維コード被覆剤は、必要に応
して例えば、レゾルシン・ホルムアルデヒド樹脂ゴムラ
テックスの分散性を改良する目的で種々の界面活性剤を
添加したり、粘度調整を目的としてリンゲニンスルポン
酸ソーダ等の増粘剤を添加たり、被着ゴム組成物との界
面状態を改良する目的でレゾルシン・ホルムアルデヒド
樹脂ゴＪ１ラテックスにカーボンブランク、加硫促進剤
、老化防止剤等のゴム用配合剤を添加することもできる
。The rubber-reinforcing glass fiber cord coating material of the present invention may contain various surfactants, if necessary, for the purpose of improving the dispersibility of the resorcinol/formaldehyde resin rubber latex, or may contain phosphorus for the purpose of adjusting the viscosity. Adding thickeners such as sodium geninsulfonate, or adding rubber such as carbon blanks, vulcanization accelerators, anti-aging agents, etc. to resorcinol formaldehyde resin Go J1 latex for the purpose of improving the interface condition with the adhered rubber composition. It is also possible to add additives.
本発明のゴム補強用硝子繊維コード被覆剤のガラス繊維
への一適用例としては、ガラス繊維への付着量が、通常
、１５〜２５％となるように含浸塗布する。この付着量
の範囲を外れると耐屈曲疲労性が問題となり望ましくな
い。好ましくは１７〜２０％である。つぎに、処理され
たガラス繊維ストランドを例えば熱風乾燥炉で通常２０
０〜３２０°Ｃで１〜３分かけて乾燥硬化させる。好ま
しくは、２３０〜２７０°Ｃで１．２〜２．５分である
。As an example of applying the rubber-reinforcing glass fiber cord coating material of the present invention to glass fibers, it is applied by impregnation so that the amount of adhesion to the glass fibers is usually 15 to 25%. If the coating amount is outside this range, bending fatigue resistance becomes a problem and is not desirable. Preferably it is 17-20%. The treated glass fiber strands are then dried, typically for 20 minutes, in a hot air drying oven, for example.
Dry and cure at 0-320°C for 1-3 minutes. Preferably, it is 1.2 to 2.5 minutes at 230 to 270°C.
その後、得られた硝子繊維ストランドを所望の本数合撚
して硝子繊維コードが得られる。Thereafter, a desired number of the obtained glass fiber strands are combined and twisted to obtain a glass fiber cord.
以下に実施例及び比較例を挙げ、本発明を更に詳しく説
明する。EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples below.
去止桝
水 ７０
部リグニン １．５部上記し
た組成で混合して本発明のゴム補強用硝子繊維コード被
覆剤を得た。Kazumasui 70
1.5 parts lignin The above-mentioned composition was mixed to obtain a glass fiber cord coating material for rubber reinforcement of the present invention.
このゴム補強用硝子繊維コード被覆剤を硝子繊維ストラ
ンド（Ｇ１５０ ３１０）に付着量が２０％となるよう
に含浸塗布し、ついで熱風乾燥炉で２５０°Ｃで２分か
けて乾燥キュアーさせた。その後、この処理された硝子
繊維ストランドを１３本合撚して硝子繊維コードを作製
した。This glass fiber cord coating material for rubber reinforcement was impregnated and applied to a glass fiber strand (G150 310) so that the adhesion amount was 20%, and then dried and cured in a hot air drying oven at 250° C. for 2 minutes. Thereafter, 13 of the treated glass fiber strands were combined and twisted to produce a glass fiber cord.
ごの硝子繊維コードを１００°Ｃでエージング後、ＭＩ
Ｔ式屈曲試験機でコー１−が切断するまでの回数で評価
した。結果を表に示す。After aging the glass fiber cord at 100°C, MI
Evaluation was made by the number of times it took for the cable to break using a T-type bending tester. The results are shown in the table.
」潰
リグニンを用いない以外は、実施例と同様にして硝子繊
維コードを作製し、実施例と同様の評価を行った。結果
を表に示す。A glass fiber cord was produced in the same manner as in the example except that crushed lignin was not used, and the same evaluation as in the example was performed. The results are shown in the table.
表
二
〔発明の効果〕
以上に詳述した通り、本発明のゴム補強用硝子繊維コー
ド被覆剤は耐熱耐老化性及び耐屈曲疲労性が優れたゴム
補強用硝子繊維を与えるものであるため、例えば自動車
エンジンルームのタイミングベルトに適用して極めて有
用であり、その工業的価値は大である。Table 2 [Effects of the Invention] As detailed above, the glass fiber cord coating for rubber reinforcement of the present invention provides glass fibers for rubber reinforcement with excellent heat resistance, aging resistance, and bending fatigue resistance. For example, it is extremely useful when applied to timing belts in automobile engine compartments, and its industrial value is great.
Claims (1)
グニンを含有することを特徴とするゴム補強用硝子繊維
コード被覆剤。A glass fiber cord coating for rubber reinforcement, characterized by containing resorcinol/formaldehyde resin rubber latex and lignin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11413588A JPH01284532A (en) | 1988-05-11 | 1988-05-11 | Coating agent for glass fiber cord for reinforcing rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11413588A JPH01284532A (en) | 1988-05-11 | 1988-05-11 | Coating agent for glass fiber cord for reinforcing rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01284532A true JPH01284532A (en) | 1989-11-15 |
Family
ID=14630015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11413588A Pending JPH01284532A (en) | 1988-05-11 | 1988-05-11 | Coating agent for glass fiber cord for reinforcing rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01284532A (en) |
-
1988
- 1988-05-11 JP JP11413588A patent/JPH01284532A/en active Pending
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