JP4899345B2 - Adhesive rubber material for bonding, composite member and method for producing the same - Google Patents
Adhesive rubber material for bonding, composite member and method for producing the same Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims description 137
- 239000005060 rubber Substances 0.000 title claims description 137
- 239000000463 material Substances 0.000 title claims description 88
- 239000000853 adhesive Substances 0.000 title claims description 21
- 230000001070 adhesive effect Effects 0.000 title claims description 21
- 239000002131 composite material Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000001816 cooling Methods 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 42
- 235000021355 Stearic acid Nutrition 0.000 claims description 21
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 21
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 21
- 239000008117 stearic acid Substances 0.000 claims description 21
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 20
- 239000000498 cooling water Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002826 coolant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 238000003915 air pollution Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 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
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Images
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、粘着性に優れ、相手方部材に容易に貼着することができる貼着用粘着性ゴム材料と、この貼着用粘着性ゴム材料を用いた複合部材及びその製造方法に関する。 The present invention relates to a sticky adhesive rubber material that is excellent in adhesiveness and can be easily attached to a counterpart member, a composite member using the sticky adhesive rubber material, and a method for producing the same.
ゴム材料は元来粘着性に優れるものであることから、その粘着性を利用して、他の材料（例えば、ゴム材料、金属、無機材料等）に張り合わせることにより製造された複合部材として、多種多様のものが製品化されている。例えば、各種タイヤ、コンベアベルト等は最も汎用されているゴム複合部材である。 Since the rubber material is originally excellent in adhesiveness, as a composite member manufactured by sticking to other materials (for example, rubber material, metal, inorganic material, etc.) using the adhesiveness, A wide variety of products have been commercialized. For example, various tires and conveyor belts are the most widely used rubber composite members.
ゴム材料は、主成分であるゴムに、補強成分としてのカーボンブラック、シリカ等の充填剤；作業性、粘弾性調整のためのオイル；酸化劣化、オゾン劣化防止のための老化防止剤；架橋材料としての加硫剤、加硫促進剤、加硫促進助剤等の各種添加剤の所定量を配合してなるゴム配合物を、用途に応じた形状に加工して製造される。加硫剤としては一般に硫黄が用いられ、加硫促進助剤として、多くの場合、ステアリン酸やステアリン酸亜鉛が用いられている。 Rubber materials include rubber as a main component, fillers such as carbon black and silica as reinforcing components; oil for adjusting workability and viscoelasticity; anti-aging agent for preventing oxidative degradation and ozone degradation; cross-linking material It is manufactured by processing a rubber compound obtained by blending predetermined amounts of various additives such as a vulcanizing agent, a vulcanization accelerator, and a vulcanization acceleration auxiliary as a shape according to the use. Sulfur is generally used as a vulcanizing agent, and stearic acid or zinc stearate is often used as a vulcanization accelerator.
また、ゴム配合物の形状加工に際しては、通常ゴム配合物を９０℃以上、好ましくは１００℃以上の高温で押出機等を用いて所定の形状に成形加工することが行われている。 Further, when processing the shape of the rubber compound, the rubber compound is usually molded into a predetermined shape using an extruder or the like at a high temperature of 90 ° C. or higher, preferably 100 ° C. or higher.
しかし、加硫促進助剤としてステアリン酸やステアリン酸亜鉛を含むゴム配合物を形状加工して得られるゴム材料は、その形状加工直後であれば十分な粘着性を維持しているものの、長時間、特に１日以上放置すると、経時により表面にステアリン酸やステアリン酸亜鉛が析出（ブルーミング）し、これがゴム材料表面を覆ってしまうことにより、ゴム材料本来の粘着性が損なわれ、相手方部材に貼着するために必要な粘着性を保持し得ないという欠点がある。 However, the rubber material obtained by shape-processing a rubber compound containing stearic acid or zinc stearate as a vulcanization accelerating aid maintains sufficient tackiness immediately after the shape processing, but for a long time Especially, if left for more than 1 day, stearic acid or zinc stearate precipitates (blooming) on the surface over time, and this covers the surface of the rubber material. There is a disadvantage that the adhesiveness required for wearing cannot be maintained.
そこで、従来においては、この粘着性低下の問題を、次の（１），（２）のようにして解決している。
（１） 経時により粘着性が低下したゴム材料の表面及び／又は相手方部材の表面に、ゴム配合物をガソリン等の速乾性の溶媒に溶かした塗布液（一般に「ゴムセメント」と呼称されている。）を塗布して、相手方部材への貼着に必要な粘着性を付与する。
（２） ポリエチレンフィルム等のフィルム状の被覆材料で、ゴム材料の表面を隙間無く覆うことにより、経時によるステアリン酸、ステアリン酸亜鉛のブルーミングを防止し、使用直前にこの被覆材料を剥がして相手方部材に貼着する。
Therefore, conventionally, the problem of the decrease in adhesiveness is solved as follows (1) and (2).
(1) A coating solution (generally referred to as “rubber cement”) in which a rubber compound is dissolved in a fast-drying solvent such as gasoline on the surface of a rubber material whose adhesiveness has decreased with time and / or the surface of a counterpart member .) Is applied to provide the adhesiveness necessary for sticking to the counterpart member.
(2) By covering the surface of the rubber material with a film-like coating material such as polyethylene film without any gaps, blooming of stearic acid and zinc stearate over time is prevented, and this coating material is peeled off immediately before use to counter the other member Adhere to.
上記（１）の方法では、ゴムセメントの塗布後、大量の溶媒を揮散させる必要があり、大気汚染、作業環境の悪化、人体への悪影響、火災の原因といった問題がある。このため、ゴムセメントの塗布のための処理コストや材料コストだけでなく、溶媒の揮散に対応した設備が必要となり、工業的に不利である。 In the method (1), it is necessary to volatilize a large amount of solvent after applying rubber cement, and there are problems such as air pollution, deterioration of the working environment, adverse effects on the human body, and causes of fire. For this reason, not only the processing cost and material cost for application | coating of rubber cement but the installation corresponding to volatilization of a solvent is needed, and it is industrially disadvantageous.
一方、ゴム材料の表面を被覆する方法では、被覆材料で覆うためにコストと手間がかかり、相手方部材に貼着する際には、被覆材料を剥がす手間があり、また、使用済被覆材料の処理の問題もある。しかも、この方法は、表面が平滑で板状のゴム材料に対しては比較的容易に適用することができるが、複雑異形形状のゴム材料に対しては、密着性良く被覆材料で覆うことは困難である。そして、被覆材料が密着していないゴム材料表面においては粘着性の低下を防止することはできない。 On the other hand, in the method of covering the surface of the rubber material, it takes a lot of cost and labor to cover with the coating material, and when sticking to the counterpart member, there is a trouble of peeling off the coating material, and processing of the used coating material There is also a problem. Moreover, this method can be applied relatively easily to a rubber material having a smooth surface and a plate-like shape, but it is not possible to cover a complex deformed rubber material with a coating material with good adhesion. Have difficulty. And on the surface of the rubber material to which the coating material is not in close contact, it is impossible to prevent a decrease in adhesiveness.
ゴム配合物の形状加工を９０℃より低い温度、例えば６０℃以下で行えば、形状加工後のゴム材料の表面へのステアリン酸やステアリン酸亜鉛のブルーミングによる粘着性低下の問題は少ないが、このような低い温度では、ゴム配合物の粘度が高いために形状加工が困難であり、生産性が著しく損なわれる。このため、９０℃以上でゴム配合物の形状加工を行い、得られたゴム材料表面の粘着性の低下に、前述の（１），（２）のような方法で対応しているのが現状である。 If the shape processing of the rubber compound is performed at a temperature lower than 90 ° C., for example, 60 ° C. or less, there is little problem of a decrease in adhesiveness due to blooming of stearic acid or zinc stearate on the surface of the rubber material after the shape processing. At such a low temperature, since the rubber compound has a high viscosity, the shape processing is difficult, and the productivity is significantly impaired. For this reason, the rubber composition is processed at a temperature of 90 ° C. or higher, and the decrease in the tackiness of the obtained rubber material surface is dealt with by the methods (1) and (2) above. It is.
なお、従来において、押出機等でゴム配合物を高温にて形状加工した後は、空冷又は更にその後水冷が行われている場合もあるが、その場合の冷却速度は高々０．５℃／秒程度であり、形状加工後、急速冷却を行うことは必要とされておらず、従って、急速冷却は適用されていない。 In addition, conventionally, after the rubber compound is shaped at a high temperature by an extruder or the like, air cooling or further water cooling may be performed after that, but the cooling rate in that case is at most 0.5 ° C./second. There is no need for rapid cooling after shape processing and therefore rapid cooling is not applied.
本発明は上記従来の実状に鑑みてなされたものであって、ステアリン酸及び／又はステアリン酸亜鉛を含むゴム配合物を９０℃以上で形状加工して得られるゴム材料であって、経時による粘着性の低下が少ない貼着用粘着性ゴム材料と、この貼着用粘着性ゴム材料を用いた複合部材及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional situation, and is a rubber material obtained by processing a rubber compound containing stearic acid and / or zinc stearate at 90 ° C. or higher, and is a pressure sensitive adhesive over time. It is an object of the present invention to provide a sticky adhesive rubber material with little deterioration in property, a composite member using the sticky adhesive rubber material, and a method for producing the same.
本発明者は、上記課題を解決すべく鋭意検討した結果、９０℃以上の温度で形状加工した後、急速冷却して得られたゴム材料は経時によるステアリン酸やステアリン酸亜鉛のブルーミングが抑えられ、この結果、粘着性の低下が防止されることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has suppressed the blooming of stearic acid and zinc stearate over time in a rubber material obtained by rapid cooling after shape processing at a temperature of 90 ° C. or higher. As a result, it was found that a decrease in adhesiveness was prevented, and the present invention was completed.
即ち、本発明は以下を要旨とするものである。 That is, the gist of the present invention is as follows.
本発明（請求項１）の貼着用粘着性ゴム材料は、ステアリン酸及び／又はステアリン酸亜鉛を含むゴム配合物を形状加工してなる貼着用粘着性ゴム材料において、該ゴム配合物を９０℃以上で形状加工した後、冷却水をシャワーした後、エアブローで乾燥することにより、１℃／秒以上の降温速度で、６０℃以下の表面温度にまで急速冷却してなることを特徴とする。 The sticky adhesive rubber material of the present invention (Claim 1) is a sticky adhesive rubber material formed by processing a rubber compound containing stearic acid and / or zinc stearate. After the shape processing as described above, after cooling water is showered and dried by air blow, it is rapidly cooled to a surface temperature of 60 ° C. or less at a temperature drop rate of 1 ° C./second or more .
請求項２の貼着用粘着性ゴム材料は、請求項１において、前記ゴム配合物を形状加工した後、２℃／秒以上の降温速度で急速冷却してなることを特徴とする。
Wear tacky rubber material bonded in 請 Motomeko 2 resides in that in
請求項３の貼着用粘着性ゴム材料は、請求項１又は２において、前記急速冷却後表面温度が７０℃以下となるように保持されていることを特徴とする。
Wear tacky rubber material bonded in 請 Motomeko 3 resides in that in
本発明（請求項４）の複合部材は、このような貼着用粘着性ゴム材料を相手側部材に貼着してなることを特徴とする。 The composite member of the present invention (invention 4 ) is characterized in that such a sticky adhesive rubber material is stuck to a counterpart member.
本発明（請求項５）の複合部材の製造方法は、ステアリン酸及び／又はステアリン酸亜鉛を含むゴム配合物を形状加工してなる貼着用粘着性ゴム材料を相手方部材に貼着して複合部材を製造する方法において、該ゴム配合物を９０℃以上で形状加工した後、冷却水をシャワーした後、エアブローで乾燥することにより、１℃／秒以上の降温速度で、６０℃以下の表面温度にまで急速冷却し、得られたゴム材料を相手方部材に貼着することを特徴とする。 The method for producing a composite member according to the present invention (Claim 5 ) is a method in which a sticky adhesive rubber material formed by processing a rubber compound containing stearic acid and / or zinc stearate is attached to a counterpart member. In this method, after the rubber compound is shaped at 90 ° C. or higher, the cooling water is showered and then dried by air blow, so that the surface temperature is 60 ° C. or lower at a temperature lowering rate of 1 ° C./second or higher. And the obtained rubber material is adhered to the counterpart member .
請求項６の複合部材の製造方法は、請求項５において、前記ゴム配合物を形状加工した後、２℃／秒以上の降温速度で急速冷却することを特徴とする。 Method for producing a composite member 請 Motomeko 6 resides in that in Claim 5, after shaping the rubber compound, characterized by rapid cooling at 2 ° C. / sec or more cooling rate.
請求項７の複合部材の製造方法は、請求項５又は６において、前記急速冷却後のゴム材料の表面温度を相手方部材に貼着するまで７０℃以下に保持することを特徴とする。 Method for producing a composite member 請 Motomeko 7, according to claim 5 or 6, characterized in that for holding the surface temperature of the rubber material after the rapid cooling below 70 ° C. until sticking to the counterpart member.
本発明によれば、９０℃以上の温度で形状加工を生産性良く行った後、冷却時に急速冷却を行うのみで、経時によるゴム材料の粘着性の低下を防止することができる。このため、ゴムセメントの塗布や、被覆材料による表面被覆といった複雑な手間とコスト、その他の工業上の不具合を引き起こすことなく、長期保管後のゴム材料であっても、これをそのまま相手方部材に貼着することができ、ゴム材料と相手方部材との貼着性に優れた複合部材を得ることができる。 According to the present invention, after shape processing is performed at a temperature of 90 ° C. or higher with high productivity, and only rapid cooling is performed at the time of cooling, it is possible to prevent a decrease in the stickiness of the rubber material over time. For this reason, even if it is a rubber material after long-term storage without causing complicated labor and cost, such as the application of rubber cement or surface coating with a coating material, and other industrial problems, it can be applied directly to the counterpart member. It is possible to obtain a composite member having excellent adhesion between the rubber material and the counterpart member.
本発明において、ゴム配合物の形状加工後の急速冷却は、１℃／秒以上、特に２℃／秒以上の降温速度で行うことが好ましい。また、この急速冷却は、ゴム材料の表面温度が６０℃以下になるまで行うことが好ましく、その後、ゴム材料の表面温度は７０℃以下となるように保持することが好ましい。 In the present invention, the rapid cooling after the shape processing of the rubber compound is preferably performed at a temperature lowering rate of 1 ° C./second or more, particularly 2 ° C./second or more. The rapid cooling is preferably performed until the surface temperature of the rubber material is 60 ° C. or lower, and thereafter, the surface temperature of the rubber material is preferably maintained so as to be 70 ° C. or lower.
以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明において、形状加工に供されるゴム配合物は、ステアリン酸及び／又はステアリン酸亜鉛を含むものであれば良く、その配合組成には特に制限はない。例えば、そのゴム成分としては、天然ゴム、ブチルゴム、ブタジエンゴム、スチレン・ブタジエン共重合ゴム等の合成ゴム、或いはこれらの２種以上のゴムのブレンド物を用いることができる。 In the present invention, the rubber compound used for the shape processing may be any compound containing stearic acid and / or zinc stearate, and the compounding composition is not particularly limited. For example, natural rubber, butyl rubber, butadiene rubber, synthetic rubber such as styrene / butadiene copolymer rubber, or a blend of two or more of these rubbers can be used as the rubber component.
このようなゴム成分に対して、加硫促進助剤としてのステアリン酸及び／又はステアリン酸亜鉛の他、カーボンブラック、シリカ、亜鉛華等の充填剤、オイル、老化防止剤、架橋剤、加硫促進剤等の添加剤が配合される。加硫剤としては硫黄を用いるのが好ましく、加硫促進剤としては、Ｍ（２−メルカプトベンゾチアゾール）、ＤＭ（ジベンゾチアジルジスルフィド）、ＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアゾールスルフェンアミド）、ＮＳ（Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド）等を用いることができる。 For such rubber components, in addition to stearic acid and / or zinc stearate as a vulcanization accelerator, fillers such as carbon black, silica, zinc white, oil, anti-aging agent, crosslinking agent, vulcanization Additives such as accelerators are blended. Sulfur is preferably used as the vulcanizing agent, and M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazole sulfenamide) is used as the vulcanizing accelerator. NS (Nt-butyl-2-benzothiazolylsulfenamide) or the like can be used.
本発明に係るゴム配合物のステアリン酸及び／又はステアリン酸亜鉛以外の配合組成は例えば次の通りであるが、何ら下記配合組成に限定されるものではない。
＜ゴム配合物配合組成＞
ゴム成分：１００重量部
カーボンブラック：２０〜１５０重量部
亜鉛華：０．５〜１０重量部
老化防止剤：０〜５重量部
硫黄：１〜１０重量部
加硫促進剤：０．２〜３重量部
The compounding composition other than stearic acid and / or zinc stearate of the rubber compound according to the present invention is, for example, as follows, but is not limited to the following compounding composition.
<Rubber compounding composition>
Rubber component: 100 parts by weight Carbon black: 20-150 parts by weight Zinc white: 0.5-10 parts by weight Anti-aging agent: 0-5 parts by weight Sulfur: 1-10 parts by weight Vulcanization accelerator: 0.2-3 Parts by weight
ゴム配合物中のステアリン酸及び／又はステアリン酸亜鉛の含有量は、過度に少ないと、そもそも経時による粘着性低下の問題も少ない。本発明による顕著な効果が得られる点においては、ゴム配合物中のステアリン酸及び／又はステアリン酸亜鉛の含有量は、ゴム成分１００重量部に対して０．５重量部以上、特に１．０重量部以上であることが好ましい。ステアリン酸及び／又はステアリン酸亜鉛は過度に多いとゴムの強度低下を引き起こすことから、通常、ゴム配合物中のゴム成分１００重量部に対して１０重量部以下、特に７重量部以下であることが好ましい。 If the content of stearic acid and / or zinc stearate in the rubber compound is excessively small, the problem of lowering the tackiness over time is also small. In terms of obtaining a remarkable effect according to the present invention, the content of stearic acid and / or zinc stearate in the rubber compound is 0.5 parts by weight or more, particularly 1.0 parts by weight with respect to 100 parts by weight of the rubber component. It is preferable that it is at least parts by weight. When the amount of stearic acid and / or zinc stearate is excessively large, the strength of the rubber is reduced. Therefore, the amount is usually 10 parts by weight or less, particularly 7 parts by weight or less based on 100 parts by weight of the rubber component in the rubber compound. Is preferred.
本発明において、９０℃以上の温度でこのようなゴム配合物を所定の形状に形状加工する。この形状加工時の温度が９０℃未満であれば、前述の如く、ゴム配合物の粘性が高く、加工性が損なわれる。ただし、形状加工温度が過度に高いとゴムの劣化等の問題を引き起こすため、形状加工温度は９０〜１３０℃、特に９５〜１２０℃程度であることが好ましい。 In the present invention, such a rubber compound is processed into a predetermined shape at a temperature of 90 ° C. or higher. If the temperature at the time of this shape processing is less than 90 ° C., as described above, the viscosity of the rubber compound is high and the workability is impaired. However, when the shape processing temperature is excessively high, problems such as deterioration of rubber are caused. Therefore, the shape processing temperature is preferably about 90 to 130 ° C, particularly about 95 to 120 ° C.
ゴム配合物の形状加工は、その加工形状に応じて任意の方法が採用されるが、一般的には押出機を用いた押出成形により、板状、棒状、波状、ノコギリ刃状、三角形状、レール状等のゴム材料を成形する方法が採用される。 The shape processing of the rubber compound may be any method depending on the processing shape, but in general, by extrusion using an extruder, a plate shape, a rod shape, a wave shape, a saw blade shape, a triangular shape, A method of molding a rubber material such as a rail is employed.
本発明においては、このようにしてゴム配合物の形状加工を行った後、急速冷却を行う。この急速冷却時の降温速度（以下「冷却速度」と称す。）は１℃／秒以上、特に２℃／秒以上とすることが好ましい。この冷却速度は速い程得られるゴム材料の経時によるステアリン酸及び／又はステアリン酸亜鉛のブルーミングが抑えられ、粘着性の低下が少ないが、冷却のためのコストや作業性の面から、一般的にはその上限は２℃／秒以下程度である。 In the present invention, after the rubber compound is shaped as described above, rapid cooling is performed. The temperature lowering rate during rapid cooling (hereinafter referred to as “cooling rate”) is preferably 1 ° C./second or more, particularly preferably 2 ° C./second or more. The faster the cooling rate, the less blooming of stearic acid and / or zinc stearate over time of the resulting rubber material is suppressed, and there is little decrease in tackiness, but in general from the cost of cooling and workability, The upper limit is about 2 ° C./second or less.
本発明では、このような急速冷却により、得られるゴム材料の表面温度が６０℃以下、特に４５℃以下にまで冷却することが好ましい。この冷却温度が６０℃よりも高いと、急速冷却を行うことによる本発明の効果を十分に得ることができない。 In the present invention, it is preferable that the surface temperature of the obtained rubber material is cooled to 60 ° C. or lower, particularly 45 ° C. or lower by such rapid cooling. When this cooling temperature is higher than 60 ° C., the effect of the present invention by performing rapid cooling cannot be sufficiently obtained.
また、このような急速冷却で、ゴム材料の表面温度を６０℃以下とした後、ゴム材料の内部からの熱でゴム材料表面の温度が上昇する場合がある。特に、断面積の大きい肉厚のゴム材料にあっては、保有熱量が大きいために、冷却後、表面温度の上昇が起こり易い。この場合、ゴム材料の表面温度が７０℃を超えると、急速冷却による本発明の効果を十分に得ることができなくなるため、ゴム材料の表面温度が７０℃を超えないように必要に応じて更に冷却を行うことが好ましい。この一旦６０℃以下の温度にまで急速冷却した後、ゴム材料の表面温度を７０℃以下に維持するための冷却速度には特に制限はない。 Further, with such rapid cooling, after the surface temperature of the rubber material is set to 60 ° C. or less, the temperature of the rubber material surface may increase due to heat from the inside of the rubber material. In particular, a thick rubber material having a large cross-sectional area has a large amount of heat, so that the surface temperature tends to increase after cooling. In this case, if the surface temperature of the rubber material exceeds 70 ° C., the effect of the present invention due to rapid cooling cannot be sufficiently obtained. Therefore, the surface temperature of the rubber material is further increased as necessary so as not to exceed 70 ° C. It is preferable to perform cooling. There is no particular limitation on the cooling rate for maintaining the surface temperature of the rubber material at 70 ° C. or lower after the rapid cooling to the temperature of 60 ° C. or lower.
本発明において、形状加工後のゴム材料の急速冷却を行う方法としては特に制限はないが押出機等の出口部において、水シャワー冷却を行うなどの方法を採用することができる。この際、形状加工後、急速冷却を開始するまでの時間が長いと、急速冷却を行うことによる本発明の効果を十分に得ることができないため、形状加工後のゴム材料は２０秒以内に、好ましくは形状加工直後に冷却を開始することが重要であり、また、形状加工時の温度に対して、ゴム材料の表面温度が９０℃以上で急速冷却を開始することが好ましい。例えば、押出機を用いた形状加工では、押出機の口金から２０ｍ以内の位置に冷却手段を設けて急速冷却を開始するようにするのが好ましい。 In the present invention, the method for rapidly cooling the rubber material after shape processing is not particularly limited, but a method such as water shower cooling at the outlet of an extruder or the like can be employed. At this time, if the time until the start of rapid cooling after shape processing is long, the effect of the present invention by performing rapid cooling cannot be sufficiently obtained, so the rubber material after shape processing is within 20 seconds, Preferably, it is important to start cooling immediately after shape processing, and it is preferable to start rapid cooling when the surface temperature of the rubber material is 90 ° C. or higher with respect to the temperature during shape processing. For example, in the shape processing using an extruder, it is preferable to start the rapid cooling by providing a cooling means at a position within 20 m from the die of the extruder.
このようにして、ゴム配合物を形状加工した後急速冷却して得られる本発明のゴム材料は、経時によるステアリン酸及び／又はステアリン酸亜鉛のブルーミングが抑えられ、このため、ステアリン酸及び／又はステアリン酸亜鉛のブルーミングによる粘着性の低下の問題が殆どない。従って、このゴム材料は長期に亘り、ゴム本来の粘着性を維持するため、他のゴム材料、金属材料、無機材料等よりなる相手方部材に対して密着性良く貼着することができ、各種材料の貼り合わせ加工等において、貼り合わせ部が剥がれることもなく、密着性に優れた複合部材を製造することができる。 In this way, the rubber material of the present invention obtained by rapid cooling after shaping the rubber compound, suppresses blooming of stearic acid and / or zinc stearate over time, and thus stearic acid and / or There is almost no problem of decrease in adhesiveness due to blooming of zinc stearate. Therefore, since this rubber material maintains the inherent adhesiveness of the rubber for a long time, it can be adhered with good adhesion to the other member made of other rubber materials, metal materials, inorganic materials, etc. In the laminating process or the like, the bonded portion is not peeled off, and a composite member having excellent adhesion can be manufactured.
以下に実験例及び実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to experimental examples and examples.
なお、以下において、用いたゴム配合物の配合組成、押出機の構成、粘着性保持率の評価方法は次の通りである。
＜ゴム配合物配合組成＞
天然ゴム（＃３）：１００重量部
カーボンブラック（ＨＡＦ）：５５重量部
亜鉛華：６重量部
ステアリン酸：４重量部
不溶性硫黄：１．５重量部
加硫促進剤（ＤＺ）：０．６重量部
（ＤＺ：Ｎ，Ｎ’−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド）
老化防止剤（６Ｃ）：０．５重量部
（６Ｃ：Ｎ−（１，３−ジメチル−ブチル）−Ｎ’−フェニル−ｐ−フェニレンジア
ミン）
In the following, the composition of the rubber compound used, the configuration of the extruder, and the evaluation method of the adhesiveness retention are as follows.
<Rubber compounding composition>
Natural rubber (# 3): 100 parts by weight Carbon black (HAF): 55 parts by weight Zinc white: 6 parts by weight Stearic acid: 4 parts by weight Insoluble sulfur: 1.5 parts by weight Vulcanization accelerator (DZ): 0.6 Parts by weight (DZ: N, N′-dicyclohexyl-2-benzothiazolylsulfenamide)
Anti-aging agent (6C): 0.5 part by weight (6C: N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine)
＜押出機構成＞
図１に示すスクリュータイプの押出機１を用いた。この押出機１の投入口２よりゴム配合物を投入し、スクリュー圧で口金３よりゴム材料を押し出した。口金３は厚さ８ｍｍ、幅２ｃｍの平板状開口である。押出温度は、投入するゴム配合物の温度、押出速度（スクリュー回転速度）、スクリュー温調温度、シリンダー温調温度、口金温度等の温度調整条件を制御することにより変化させることができる。
<Extruder configuration>
A
口金３から押し出された平板状のゴム材料Ｇには、口金３から１．５ｍの位置（この位置においては、押し出されたゴム材料Ｇの表面温度は、押出温度とほぼ同等である。）からゴム材料Ｇに最大で５ｍの長さ範囲に渡って冷却媒体（１０〜４０℃の範囲内で温度制御された冷却水）を冷却媒体噴出口４よりシャワー散布した。５は冷却媒体回収口である。冷却水の温度及び散布量を制御することにより冷却速度を制御することができる。 The flat rubber material G extruded from the base 3 has a position of 1.5 m from the base 3 (in this position, the surface temperature of the extruded rubber material G is substantially equal to the extrusion temperature). A cooling medium (cooling water whose temperature was controlled within a range of 10 to 40 ° C.) was sprayed on the rubber material G from the cooling medium outlet 4 over a length range of 5 m at the maximum. Reference numeral 5 denotes a cooling medium recovery port. The cooling rate can be controlled by controlling the temperature of the cooling water and the amount of sprayed water.
冷却水をシャワーした後のゴム材料Ｇは、エアブロー口６からのエアブローで乾燥される。 The rubber material G after showering the cooling water is dried by air blow from the air blow port 6.
７Ａ，７Ｂはゴム配合物の表面温度を測定するための温度計であり、押出温度は、温度計７Ａの測定温度とし、冷却速度は、温度計７Ｂの測定温度と温度計７Ａの測定温度との差と、温度計７Ａの位置から温度計７Ｂの位置までに到達するまでの時間から求めた。
7A and 7B are thermometers for measuring the surface temperature of the rubber compound, the extrusion temperature is the measurement temperature of the
＜粘着性保持率の評価方法＞
押出機で押し出されたゴム材料を押出後６時間経過後にステンレス板の板面に密着させた後、ステンレス板を引張り、ゴム材料と剥がれるときの最大の力を測定し初期粘着力Ｆ０とし、４日間放置後のゴム材料について同様に測定した値を経時粘着力ＦＸとし、下記式で算出した粘着指数を粘着性保持率の評価値とした。この値が大きい程、経時による粘着性の低下度合が少ない。
粘着指数＝（ＮＸ／Ｎ０）×１００
<Method for evaluating adhesive retention>
After the rubber material extruded by the extruder after 6 hours after extrusion passed in close contact with the plate surface of the stainless steel plate, pulling the stainless steel plate, to measure the maximum force when peeling the rubber material as the initial adhesive force F 0, the value measured in the same manner for the rubber material after standing for 4 days and time adhesive strength F X, the adhesive index calculated by the following formula and the evaluation value of the tack retention. The larger this value, the less the degree of decrease in tackiness over time.
Adhesion index = (N X / N 0 ) × 100
実験例１
押出機でゴム配合物を押し出す際、温度調整条件を制御することにより押出機内のゴム配合物温度を制御し、口金から押し出されたゴム材料の表面温度が５０〜１２０℃の各温度となるようにしてそれぞれゴム材料を押し出し、押出直後のゴム材料を表面温度が２５℃となるまで、約０．５℃／秒以下の冷却速度で緩速冷却した。
Experimental example 1
When extruding a rubber compound with an extruder, the temperature of the rubber compound in the extruder is controlled by controlling the temperature adjustment conditions so that the surface temperature of the rubber material extruded from the die becomes 50 to 120 ° C. Each rubber material was extruded, and the rubber material immediately after extrusion was slowly cooled at a cooling rate of about 0.5 ° C./second or less until the surface temperature reached 25 ° C.
各ゴム材料について、粘着性の評価を行い、結果を図２に示した。 Each rubber material was evaluated for adhesiveness, and the results are shown in FIG.
図２より、押出温度（形状加工温度）９０℃以上、特に１００℃以上で得られたゴム材料は、通常の冷却条件では経時による粘着性の低下が著しいことが分かる。なお、６０℃程度の押出温度で得られたゴム材料では、経時による粘着性の低下の問題はないが、この温度では、ゴム配合物の粘性が高く、生産性に劣るため、実用的ではない。 From FIG. 2, it can be seen that the rubber material obtained at an extrusion temperature (shape processing temperature) of 90 ° C. or higher, particularly 100 ° C. or higher, has a remarkable decrease in adhesiveness over time under normal cooling conditions. In addition, the rubber material obtained at an extrusion temperature of about 60 ° C. does not have a problem of a decrease in adhesiveness over time, but at this temperature, the rubber compound is high in viscosity and inferior in productivity, so it is not practical. .
実施例１
押出機でゴム配合物を押し出す際、温度調整条件を制御することにより押出機内のゴム配合物温度を制御し、口金から押し出されたゴム材料の表面温度が１１０〜１１５℃となるようにゴム材料を押し出し、押出直後のゴム材料を表面温度が６０℃以下となるように、０．１〜５℃／秒の各冷却速度で冷却した。なお、表面温度が６０℃以下にまで冷却した後は、表面温度が上がらないように更に空気中で徐冷した。
Example 1
When extruding a rubber compound with an extruder, the temperature of the rubber compound in the extruder is controlled by controlling the temperature adjustment conditions, so that the surface temperature of the rubber material extruded from the die becomes 110 to 115 ° C. The rubber material immediately after extrusion was cooled at a cooling rate of 0.1 to 5 ° C./second so that the surface temperature was 60 ° C. or less. After cooling the surface temperature to 60 ° C. or lower, it was further gradually cooled in air so that the surface temperature did not rise.
各ゴム材料について、粘着性の評価を行い、結果を図３に示した。 Each rubber material was evaluated for adhesiveness, and the results are shown in FIG.
なお、図３において、ａ〜ｈの各点の冷却速度は以下の通りである。
ａ：０．１２℃／秒
ｂ：０．２１℃／秒
ｃ：０．３３℃／秒
ｄ：０．５０℃／秒
ｅ：０．９０℃／秒
ｆ：１．０℃／秒
ｇ：１．８℃／秒
ｈ：３．１℃／秒
In addition, in FIG. 3, the cooling rate of each point of ah is as follows.
a: 0.12 ° C / second b: 0.21 ° C / second c: 0.33 ° C / second d: 0.50 ° C / second e: 0.90 ° C / second f: 1.0 ° C / second g: 1.8 ° C./second h: 3.1 ° C./second
図３より、押出後の冷却速度が０．１〜０．５℃／秒程度の緩速冷却では、粘着性の低下が著しく、粘着性は押出直後の１／１０程度になってしまうが、１℃／秒以上、特に２℃／秒以上の急速冷却を行うことにより、粘着性の低下を抑えることができ、４日後の粘着力は、急速冷却を行わない場合の５〜６倍に達することが分かる。 From FIG. 3, in the slow cooling at a cooling rate after extrusion of about 0.1 to 0.5 ° C./second, the decrease in adhesiveness is remarkable, and the adhesiveness becomes about 1/10 immediately after extrusion, By performing rapid cooling at 1 ° C./second or more, particularly at 2 ° C./second or more, a decrease in adhesiveness can be suppressed, and the adhesive strength after 4 days reaches 5 to 6 times that when rapid cooling is not performed. I understand that.
本発明は、タイヤ、コンベアーベルト、ゴムクローラ等の各種のゴム複合部材に有効に適用される。 The present invention is effectively applied to various rubber composite members such as tires, conveyor belts, rubber crawlers and the like.
１ 押出機
２ 投入口
３ 口金
４ 冷却媒体噴出口
５ 冷却媒体回収口
６ エアブロー口
７Ａ，７Ｂ 温度計
Ｇ ゴム材料
DESCRIPTION OF
Claims (7)
該ゴム配合物を９０℃以上で形状加工した後、冷却水をシャワーした後、エアブローで乾燥することにより、１℃／秒以上の降温速度で、６０℃以下の表面温度にまで急速冷却してなることを特徴とする貼着用粘着性ゴム材料。 In a sticky adhesive rubber material formed by shaping a rubber compound containing stearic acid and / or zinc stearate,
After the rubber compound is shaped at 90 ° C. or higher, the cooling water is showered and then dried by air blow to rapidly cool to a surface temperature of 60 ° C. or lower at a temperature drop rate of 1 ° C./second or higher. An adhesive rubber material for sticking, characterized in that
該ゴム配合物を９０℃以上で形状加工した後、冷却水をシャワーした後、エアブローで乾燥することにより、１℃／秒以上の降温速度で、６０℃以下の表面温度にまで急速冷却し、得られたゴム材料を相手方部材に貼着することを特徴とする複合部材の製造方法。 In a method of manufacturing a composite member by sticking a sticky adhesive rubber material formed by processing a rubber compound containing stearic acid and / or zinc stearate to a counterpart member,
After the rubber compound is shaped at 90 ° C. or higher, after cooling water is showered, it is rapidly cooled to a surface temperature of 60 ° C. or lower at a temperature drop rate of 1 ° C./second or more by drying with air blow , A method for producing a composite member, comprising sticking the obtained rubber material to a counterpart member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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