JP4811207B2 - Heat resistant rubber hose - Google Patents

Heat resistant rubber hose Download PDF

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JP4811207B2
JP4811207B2 JP2006247636A JP2006247636A JP4811207B2 JP 4811207 B2 JP4811207 B2 JP 4811207B2 JP 2006247636 A JP2006247636 A JP 2006247636A JP 2006247636 A JP2006247636 A JP 2006247636A JP 4811207 B2 JP4811207 B2 JP 4811207B2
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rubber
rubber layer
outer tube
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silicone rubber
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英一 栗本
靖 中原
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Toyoda Gosei Co Ltd
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Description

本発明は、自動車のエンジンルーム内で使用されるエアー系の耐熱ゴムホースに関するものである。   The present invention relates to an air-based heat resistant rubber hose used in an engine room of an automobile.

自動車のエンジルーム内の高熱化に伴い、エアー系ホースも耐熱性が要求されてきている。従来のアクリルゴムでの耐熱では不十分となり、200℃近辺の耐熱性を確保できる材料への置換が必要である。耐エンジンオイル性の確保も考慮するとフッ素ゴムが優れているが、高コストである。 With the increase in heat in the engine room of automobiles, air hoses are also required to have heat resistance. Conventional heat resistance with acrylic rubber is insufficient, and replacement with a material that can ensure heat resistance around 200 ° C. is necessary. Considering ensuring engine oil resistance, fluororubber is superior, but it is expensive.

内管ゴム層をフッ素ゴム、外管ゴム層をシリコーンゴムとし、補強繊維として耐熱性のあるアラミド繊維を使用するホース構成が特許文献1、特許文献2に記載されている。しかし、これらのホースはシリコーンゴムとアラミド繊維との接着力が不十分であり、耐圧性・耐久性試験での糸抜けと言う問題が生じている。
特開2000−193152 WO2003/098088
Patent Documents 1 and 2 describe a hose configuration in which an inner tube rubber layer is made of fluorine rubber, an outer tube rubber layer is made of silicone rubber, and heat-resistant aramid fibers are used as reinforcing fibers. However, these hoses have insufficient adhesive strength between the silicone rubber and the aramid fibers, which causes a problem of yarn removal in the pressure resistance / durability test.
JP 2000-193152 A WO2003 / 098088

本発明の目的は、200℃近辺の高温化での使用においてもシリコーンゴムとアラミド繊維との接着力が確保できる耐熱ゴムホースを提供することにある。 An object of the present invention is to provide a heat-resistant rubber hose capable of ensuring the adhesive force between silicone rubber and aramid fiber even when used at a high temperature around 200 ° C.

内管ゴム層、外管第1ゴム層、補強層、外管第2ゴム層の順で積層された積層体からなる耐熱ゴムホースにおいて、内管ゴム層はフッ素ゴム組成物、外管第1ゴム層と外管第2ゴム層はシリコーンゴム組成物からなり、補強層はアミノ基あるいはエポキシ基を有するシランカップリング剤を含む溶液に浸漬したアラミド繊維からなる耐熱ゴムホース。 In a heat resistant rubber hose comprising a laminate in which an inner tube rubber layer, an outer tube first rubber layer, a reinforcing layer, and an outer tube second rubber layer are laminated in this order, the inner tube rubber layer is a fluororubber composition, and the outer tube first rubber. The heat-resistant rubber hose is made of an aramid fiber immersed in a solution containing a silane coupling agent having an amino group or an epoxy group .

フッ素ゴム組成物
フッ素ゴムとしては、フッ化ビニリデン−ヘキサフルオロプロピレン弾性共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン弾性共重合体等が挙げられる。フッ素ゴムは、1種単独で用いてもよく、2種以上を併用してもよい。なかでも、耐薬品性に優れるフッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン弾性共重合体が好ましい。
Fluororubber composition Examples of the fluororubber include vinylidene fluoride-hexafluoropropylene elastic copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene elastic copolymer, and the like. A fluororubber may be used individually by 1 type, and may use 2 or more types together. Among these, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene elastic copolymer having excellent chemical resistance is preferable.

フッ素ゴムの配合剤としては補強剤、充填剤、加工助剤があり、また、加硫方法としては、過酸化物加硫、ポリオール加硫、アミン加硫が挙げられる。 Examples of the compounding agent for fluororubber include reinforcing agents, fillers, and processing aids. Examples of vulcanization methods include peroxide vulcanization, polyol vulcanization, and amine vulcanization.

シリコーンゴム組成物
シリコーンゴムとしては、ジメチルシリコーンゴム、メチルビニルシリコーンゴム、メチルフェニルシリコーンゴム、フルオロシリコーンゴム等が挙げられる。特に、ジメチルシリコーンゴムが好ましい。
Silicone rubber composition Examples of the silicone rubber include dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl silicone rubber, and fluorosilicone rubber. In particular, dimethyl silicone rubber is preferable.

シリコーンゴムの配合剤としては補強剤、充填剤、加工助剤があり、また、加硫方法としては、過酸化物加硫が好ましい。 Silicone rubber compounding agents include reinforcing agents, fillers and processing aids, and peroxide vulcanization is preferred as the vulcanization method.

アラミド繊維
アラミド繊維は分子骨格が直鎖状のパラ型タイプ、ジグザグ状のメタ型タイプがある。パラ型タイプとしてはポリパラフェニレンテレフタルアミドやコポリパラフェニレン・3,4オキシジフェニレンテレフタルアミドがあり、メタ型タイプとしてはポリメタフェニレンイソフタルアミドがある。
Aramid fibers Aramid fibers include para-types with a linear molecular skeleton and zigzag meta-types. The para type includes polyparaphenylene terephthalamide and copolyparaphenylene 3,4 oxydiphenylene terephthalamide, and the meta type includes polymetaphenylene isophthalamide.

シランカップリング剤
シランカップリング剤は有機官能基、加水分解性基を持ち、有機官能基としてはビニル基、エポキシ基、メタクリル基、アミノ基、メルカプト基などが挙げられる。一方、加水分解性基としてはクロル基、アルコキシ基、アセトキシ基、イソプロペノキシ基、アミノ基などがあるがアルコキシ基がほとんどである。
Silane coupling agent The silane coupling agent has an organic functional group and a hydrolyzable group, and examples of the organic functional group include a vinyl group, an epoxy group, a methacryl group, an amino group, and a mercapto group. On the other hand, hydrolyzable groups include a chloro group, an alkoxy group, an acetoxy group, an isopropenoxy group, an amino group, and the like, but most are alkoxy groups.

耐熱ゴムホースの構成
フッ素ゴム組成物からなる内管ゴム層肉厚は0.5mm〜1mmであり、シリコーンゴム組成物からなる外管第1ゴム層肉厚は0.5mm〜1.5mmで、外管第2ゴム層肉厚は1.5mm〜2.5mmである。内管ゴム層と外管第1ゴム層は加硫接着しており接着剤層は特に必要ない。外管第1ゴム層と外管第2ゴム層間はアラミド繊維で補強されている。
Structure of heat resistant rubber hose The inner tube rubber layer thickness made of fluororubber composition is 0.5 mm to 1 mm, and the outer tube first rubber layer thickness made of silicone rubber composition is 0.5 mm to 1.5 mm. The tube second rubber layer thickness is 1.5 mm to 2.5 mm. The inner tube rubber layer and the outer tube first rubber layer are vulcanized and bonded, and no adhesive layer is required. The outer tube first rubber layer and the outer tube second rubber layer are reinforced with aramid fibers.

本発明の耐熱ゴムホースは、200℃近辺の高温化での使用においてもシリコーンゴムとアラミド繊維との接着力が確保できる。 The heat-resistant rubber hose of the present invention can secure the adhesive force between silicone rubber and aramid fiber even when used at a high temperature around 200 ° C.

本発明の好ましい態様は、内管ゴム層、外管第1ゴム層、補強繊維層、外管第2ゴム層の順で積層された積層体からなる耐熱ゴムホースにおいて、
内管ゴム層はフッ素ゴム組成物、外管第1ゴム層と外管第2ゴム層はシリコーンゴム組成物からなり、補強繊維層はシランカップリング剤を含有したアラミド繊維からなる耐熱ゴムホースである。
A preferred embodiment of the present invention is a heat resistant rubber hose comprising a laminate in which an inner tube rubber layer, an outer tube first rubber layer, a reinforcing fiber layer, and an outer tube second rubber layer are laminated in this order.
The inner tube rubber layer is a fluororubber composition, the outer tube first rubber layer and the outer tube second rubber layer are made of a silicone rubber composition, and the reinforcing fiber layer is a heat resistant rubber hose made of an aramid fiber containing a silane coupling agent. .

表-1に記したシランカップリング剤のトルエン溶液(濃度2wt%)にアラミド繊維(コーネックス20/4)を常温23℃にて30秒間浸漬し、取出し後に150℃×30秒間乾燥する。
素抜け距離が55mmになるように、アラミド繊維を過酸化物加硫系シリコーンゴムシート(硬度Hs:75〜80)で挟み込み、160℃×30分間スチーム加硫してテストピースを作成する。シリコーンゴムとアラミド繊維の接着力を素抜け力で評価するため、引張り試験機で繊維1本を引張り、その抜け力を測定する。(引張り速度30mm/分)
Aramid fibers (Conex 20/4) are immersed in a toluene solution (concentration 2 wt%) of the silane coupling agent shown in Table 1 for 30 seconds at a room temperature of 23 ° C., and are taken out and dried at 150 ° C. for 30 seconds.
Aramid fibers are sandwiched between peroxide vulcanized silicone rubber sheets (hardness Hs: 75-80) so that the unplugged distance is 55 mm, and steam vulcanized at 160 ° C. for 30 minutes to prepare a test piece. In order to evaluate the adhesive strength between silicone rubber and aramid fibers by the pull-out force, one fiber is pulled with a tensile tester and the pull-out force is measured. (Tensile speed 30mm / min)

その結果を表-1に記す。シランカップリング剤を含有したアラミド繊維はシリコーンゴムとの素抜け力は高いが、シランカップリング剤を含有しないアラミド繊維は素抜け力が小さい。 The results are shown in Table-1. An aramid fiber containing a silane coupling agent has a high pull-out power with silicone rubber, but an aramid fiber not containing a silane coupling agent has a low pull-out power.

また、製品性能試験のため、ポリオール・過酸化物加硫の3元系フッ素ゴム(硬度Hs:70〜80)を内管ゴム層とし、過酸化物加硫系シリコーンゴム(硬度Hs:75〜80)を外管第1ゴム層と外管第2ゴム層とし、アラミド繊維を補強層として試験用ホースを作成する。 For product performance testing, polyol-peroxide vulcanized ternary fluororubber (hardness Hs: 70-80) is used as the inner rubber layer, and peroxide vulcanized silicone rubber (hardness Hs: 75- 80) is used as an outer tube first rubber layer and an outer tube second rubber layer, and an aramid fiber is used as a reinforcing layer to prepare a test hose.

製品性能試験として素抜け力を測定する。素抜け距離が55mmになるようにホースからテストピースを切り出し、引張り試験機で繊維2本を同時に引張り、その抜け力を測定する。 Measure unplugging force as a product performance test. A test piece is cut out from the hose so that the unplugging distance is 55 mm, and two fibers are simultaneously pulled with a tensile tester, and the pulling force is measured.

その結果を表-2に記す。シランカップリング剤を含有したアラミド繊維はシリコーンゴムとの素抜け力が高く、シリコーンゴムの凝集破壊を生じている。一方、シランカップリング剤を含有しないアラミド繊維は素抜け力が小さく、
シリコーンゴムと繊維間での界面剥離を生じている。
The results are shown in Table-2. Aramid fibers containing a silane coupling agent have a high pull-out force with silicone rubber, and cause cohesive failure of the silicone rubber. On the other hand, an aramid fiber not containing a silane coupling agent has a small unplugging force,
Interfacial peeling occurs between the silicone rubber and the fiber.

(表1)

Figure 0004811207
(Table 1)
Figure 0004811207

(表2)

Figure 0004811207

(Table 2)
Figure 0004811207

Claims (1)

内管ゴム層、外管第1ゴム層、補強層、外管第2ゴム層の順で積層された積層体からなる耐熱ゴムホースにおいて、内管ゴム層はフッ素ゴム組成物、外管第1ゴム層と外管第2ゴム層はシリコーンゴム組成物からなり、補強層はアミノ基あるいはエポキシ基を有するシランカップリング剤を含む溶液に浸漬したアラミド繊維からなる耐熱ゴムホース。 In a heat resistant rubber hose comprising a laminate in which an inner tube rubber layer, an outer tube first rubber layer, a reinforcing layer, and an outer tube second rubber layer are laminated in this order, the inner tube rubber layer is a fluororubber composition, and the outer tube first rubber. The heat-resistant rubber hose is made of an aramid fiber immersed in a solution containing a silane coupling agent having an amino group or an epoxy group .
JP2006247636A 2006-09-13 2006-09-13 Heat resistant rubber hose Active JP4811207B2 (en)

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CN101713151A (en) * 2008-10-06 2010-05-26 E.I.内穆尔杜邦公司 Composite reinforcing material, manufacture method and applications thereof
JP2013221580A (en) * 2012-04-17 2013-10-28 Nissan Motor Co Ltd Fastening structure of pipe for supercharger system
KR101716674B1 (en) * 2015-10-12 2017-03-15 주식회사 백일 Process Of Producing Aramid Short Staple Dipcord For Extrusiontype High Temperature And High Pressure rubber hose

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JPH09136364A (en) * 1995-11-15 1997-05-27 Yokohama Rubber Co Ltd:The High-pressure flexible hose
JP2003214566A (en) * 2001-11-14 2003-07-30 Marugo Rubber Ind Co Ltd Rubber hose and method of manufacture
JP4183227B2 (en) * 2001-11-14 2008-11-19 丸五ゴム工業株式会社 Rubber hose

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