JP2008195040A - Fuel-system rubber hose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel-system rubber hose which is superior in heat resistance, low extractability, resistance to acidic products obtained by cracking FAME-mixture gas oil, durability, etc. , and has high interlayer adhesion. <P>SOLUTION: The rubber hose has the tubular inner layer 1 and the rubber-made outer layer 2 which is formed in contact with the peripheral surface of the inner later 1. The inner layer 1 is formed by using a rubber composition containing iodine-containing fluororubber (A), an organic peroxide crosslinking agent (B), triallyl isocyanurate (C), and a p-quinone dioxime compound (D) as indispensable components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fuel rubber hose used for transportation of fuel such as automobiles (gasoline, alcohol-mixed gasoline, CNG, diesel fuel, etc.).

  Due to increasing global environmental awareness, regulations on the transpiration of hydrocarbons from automotive fuel hoses have been tightened, and in particular, strict transpiration regulations have been legislated in the United States. Under such circumstances, in recent years, exhaust gas regulations for diesel vehicles have been strengthened, and the introduction of a new engine system (common rail fuel injection system) corresponding to that has been in full swing. In the common rail fuel injection system, the control system is programmed to increase combustion efficiency for the purpose of low exhaust gas, and fuel is injected at a high temperature and high pressure during operation of the engine. The fuel hose used in the above is required to have higher heat resistance than before. In addition, such an increase in fuel temperature induces the generation of acid accompanying the decomposition of sour gasoline and FAME (fatty acid esterified) mixed light oil, so that the fuel system hose is also required to have such resistance. Also, in order to increase combustion efficiency, the fuel injection injector nozzle part has become more precise than before, so the extract from the hose, which has had little effect in the past, clogs the nozzle part. There are concerns to cause. Therefore, low extractability of the hose is also required.

Conventionally, this type of automotive fuel hose has used various hoses made by laminating and integrating a plurality of layers, including a fluororubber layer with excellent fuel permeability (barrier properties). A laminated hose has been proposed in which the inner layer is the outer layer and the epichlorohydrin rubber layer is the outer layer (see Patent Document 1).
JP-A-10-264314

  When the above laminated hose is used, for example, in the fuel hose application in the common rail fuel injection system described above, the polyol (vulcanized rubber layer) is usually vulcanized from the viewpoint of excellent workability. Fluorine-based rubbers have generally been used. However, polyol vulcanized fluorine rubber is inferior in acid product resistance due to decomposition of FAME blended light oil, and generation of an extract (dropping out of acid acceptor etc.) is also observed. Therefore, the injector nozzle in the fuel injection system There is a concern of causing clogging. In addition, the polyol vulcanized fluorine-based rubber has a problem that it is inferior in resistance (amine resistance) to an additive (polyamine) contained in gasoline. Furthermore, in such a laminated hose, since the adhesiveness between the layers greatly affects the hose performance, a high interlayer adhesive force is required.

  The present invention has been made in view of such circumstances, and is superior in heat resistance, low extractability and acid product resistance due to decomposition of FAME mixed gas oil, and has high interlayer adhesion and excellent durability. The purpose is to provide.

In order to achieve the above object, a fuel rubber hose of the present invention is a fuel rubber hose comprising a tubular inner layer and a rubber outer layer provided in contact with the outer peripheral surface, wherein the inner layer is the following ( It takes the structure that it is formed using the rubber composition which has A)-(D) as an essential component.
(A) Iodine-containing fluororubber.
(B) Organic peroxide crosslinking agent.
(C) Triallyl isocyanurate.
(D) p-quinone dioxime compound.

That is, the present inventor has intensively studied to solve the above problems. In the course of the research, it was confirmed that it was advantageous to make the inner layer of the hose into a fluorine rubber (FKM) layer having excellent barrier properties. At present, only the use of polyol vulcanized FKM has been established, but as described above, it was also confirmed that the polyol vulcanized one is difficult to adopt from the viewpoint of low extractability and acid resistance. Therefore, the present inventor has recalled that the organic peroxide vulcanization (peroxide crosslinking) FKM is used as the inner layer material, thereby eliminating the problems of low extractability and acid resistance. However, the organic peroxide vulcanization system FKM is liable to cause solvent cracks in the fuel, and further has poor adhesion to the outer rubber (outer layer). The present inventor has repeated further studies for improvement of crack growth resistance (solvent cracking resistance) and the interlayer adhesion or the like, so that as the inner layer of the forming material, using iodine-containing fluororubber, thereto, a co-crosslinking As an agent, triallyl isocyanurate and a p-quinonedioxime compound were added and vulcanized with an organic peroxide. As a result, excellent interlayer adhesion and tensile permanent strain (sealability) were obtained. Since the p-quinonedioxime compound is partially intervened in the co-crosslinking portion by isocyanurate to form a moderately crosslinked structure and relieve stress during stretching, the above crack progressability (solvent crack property) The present inventors have found that problems can be solved and have reached the present invention.

  As described above, the fuel rubber hose of the present invention includes a tubular inner layer (fluororubber layer) and a rubber outer layer provided in contact with the outer peripheral surface, and the inner layer includes iodine-containing fluororubber, It is formed using the rubber composition which has an organic peroxide crosslinking agent, triallyl isocyanurate, and a p-quinone dioxime compound as essential components. Therefore, the fuel rubber hose of the present invention has excellent heat resistance and low permeability, and has high interlayer reliability and tensile permanent strain, so that it is extremely excellent in quality reliability. Furthermore, it is excellent in acid resistance, low extractability and the like. This makes it possible to exhibit excellent performance as a fuel hose for a common rail fuel injection system (new diesel engine system) that requires high temperature and high pressure resistance.

  In particular, when the inner layer is formed using a rubber composition containing magnesium oxide (MgO) as an acid acceptor together with the essential components, the magnesium oxide functions as a propellant for deHF (hydrofluoric acid). , Interlayer adhesion becomes higher.

  Further, when the inner layer is formed using a rubber composition containing dipentamethylene thiuram tetrasulfide as a scorch inhibitor together with the essential components, the scorch property of the inner layer is improved, and extrusion processability and interlayer adhesion are improved. It becomes more excellent in sex.

  Furthermore, the rubber outer layer is made of epichlorohydrin-ethylene oxide copolymer rubber (ECO), acrylonitrile-butadiene rubber / polyvinyl chloride blend rubber (NBR-PVC), acrylic rubber (ACM), ethylene-acrylic rubber (AEM). When formed using chlorosulfonated polyethylene (CSM) or the like, the inner layer formed by organic peroxide vulcanization can exhibit particularly excellent performance as a fuel hose for automobiles. And better interlayer adhesion.

  When the rubber outer layer is formed using ECO or NBR-PVC, 1,8-diazabicyclo- (5,4,0) -undecene-7 (DBU) is contained in the rubber outer layer material. ) Or a weak acid salt thereof, the interlayer adhesion with the inner layer is further improved.

  Next, an embodiment of the present invention will be described.

  The fuel-based rubber hose of the present invention is characterized in that the inner layer is formed using a fluoro rubber containing a specific component. For example, as shown in FIG. 1, the layer structure includes a two-layer structure including an inner layer (fluororubber layer) 1 and a rubber outer layer 2 provided in contact with the outer peripheral surface thereof. Further, as shown in FIG. 2, a reinforcing yarn layer 3 is formed on the outer peripheral surface of the rubber outer layer 2, and a rubber outermost layer 4 is formed on the outer peripheral surface of the reinforcing yarn layer 3. May be configured. As shown in FIG. 3, a reinforcing yarn layer 3 is provided between the inner layer 1 and the rubber outer layer 2, and the adhesiveness between the inner layer 1 and the outer layer 2 through the weave of the reinforcing yarn layer 3. It is good also as a structure which can obtain (interlayer adhesiveness).

  In the present invention, as described above, the inner layer 1 includes an iodine-containing fluororubber [component (A)], an organic peroxide crosslinking agent [component (B)], and triallyl isocyanurate [(C ) Component] and a p-quinonedioxime compound [component (D)] are used.

  Here, the iodine-containing fluororubber as the component (A) refers to a fluorinated polymer that has rubber elasticity at room temperature when vulcanized. Conventionally known fluororubbers are included, and typical fluororubbers include vinylidene fluoride / hexafluoropropylene, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene, and vinylidene fluoride / chlorotrifluoroethylene. Fluoro rubbers such as tetrafluoroethylene / propylene, hexafluoropropylene / ethylene, perfluoroalkyl vinyl ether / olefin (tetrafluoroethylene, ethylene, etc.), fluorosilicone, fluorophosphazene, and the like. Examples of iodine-containing fluororubber are described in, for example, Japanese Patent Publication No. 5-63482 and Japanese Patent Laid-Open No. 7-315234. That is, the iodine-containing fluororubber contains an iodine-containing compound [for example, perfluoro (6,6-dihydro-6-iodo-3-oxa-) in addition to the above-mentioned fluororubber monomer (for example, vinylidene fluoride). 1-hexene), perfluoro (5-iodo-3-oxa-1-pentene, etc.)] and the like. The iodine-containing fluororubber may be used alone or in combination of two or more. Among these, from the viewpoint of interlayer adhesion by organic peroxide crosslinking and solvent cracking properties, the above-mentioned fluororubber monomers are vinylidene fluoride / hexafluoropropylene, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene. Are preferred.

  In addition, as a commercial item of the iodine containing fluororubber of the said (A) component, Daiel G901 etc. by Daikin Industries, Ltd. can be used as a suitable thing, for example.

  Examples of the organic peroxide crosslinking agent [component (B)] used together with the component (A) include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. -Bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) butane, n-butyl-4, Peroxyketals such as 4-bis (t-butylperoxy) valerate, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide α, α′-bis (t-butylperoxy-m-isopropyl) benzene, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, dialkyl peroxides, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl Diacyl peroxides such as peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, and t-butyl peroxide Oxyacetate, t-butyl peroxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di ( Benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, peroxyesters such as cumylperoxyoctate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydro And hydroperoxides such as peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3, -tetramethylbutyl peroxide, and the like. These may be used alone or in combination of two or more.

  The blending ratio of the component (B) is set in the range of 0.1 to 5 parts with respect to 100 parts by weight (hereinafter abbreviated as “part”) of the iodine-containing fluororubber of the component (A). Preferably, it is in the range of 0.2 to 4 parts. That is, if the organic peroxide cross-linking agent [component (B)] is less than 0.1 part, the cross-linking is insufficient and the hose strength and sealability are deteriorated. This is because if it exceeds 5 parts, it becomes too hard and the flexibility of the hose tends to be impaired.

  In the present invention, a polyfunctional monomer such as triallyl isocyanurate [(C) component] and p-quinonedioxime compound [(D) component] is added to the inner layer together with the components (A) and (B). 1 is used as an essential component of the rubber composition for forming 1.

  The p-quinonedioxime compound as the component (D) is preferably a compound represented by the following general formula (1), specifically, p-benzoquinonedioxime, pp'-dibenzoylquinone. And dioxime. Such a p-quinonedioxime compound is advantageously used in the present invention because it does not cause problems such as sublimation, difficulty in crosslinking control, odor problems, and interlayer foaming often found in conventional co-crosslinking agents. .

  Further, the blending ratio of the component (C) and the component (D) to the component (A) (iodine-containing fluororubber) is not particularly limited as long as the blend ratio is satisfied. From the viewpoint of strength and sealing properties, the component (C) is preferably set in a range of 0.1 to 2 parts, more preferably 0.2 to 1 with respect to 100 parts of the component (A). .5 parts range. From the same viewpoint, the component (D) is preferably set in the range of 0.05 to 2 parts, more preferably in the range of 0.1 to 1 part, with respect to 100 parts of the component (A). It is.

  By the way, in the rubber composition for forming the inner layer 1 in the fuel rubber hose of the present invention, in addition to the components (A) to (D) as essential components, magnesium oxide [(( E) component] is preferable because this magnesium oxide functions as a propellant for deHF (hydrofluoric acid) and the interlaminar adhesion becomes higher.

  The blending ratio of the component (E) is preferably set in the range of 0.1 to 20 parts, more preferably 1 to 10 parts with respect to 100 parts of the iodine-containing fluororubber of the component (A). It is a range. That is, by including magnesium oxide [(E) component] within this range, an improvement effect such as interlayer adhesion can be obtained.

  In addition to the above components (A) to (D), if necessary, dipentamethylene thiuram tetrasulfide [component (F)] is added as a scorch inhibitor, so that the scorch property of the inner layer is improved. It is preferable because the processability and interlayer adhesion become more excellent.

  The blending ratio of the component (F) is preferably set in the range of 0.05 to 2 parts, more preferably 0.1 to 1 with respect to 100 parts of the iodine-containing fluororubber of the component (A). Part range. That is, by including dipentamethylene thiuram tetrasulfide [component (F)] within this range, an effect of improving the scorch property can be obtained.

  The material for the inner layer 1 may contain carbon black, processing aids, coloring agents, and the like as necessary together with the above components.

  The material for forming the outer layer 2 made of rubber formed on the outer peripheral surface of the inner layer 1 is not particularly limited, but is particularly a blend of epichlorohydrin-ethylene oxide copolymer rubber (ECO), acrylonitrile-butadiene rubber and polyvinyl chloride. When formed using rubber (NBR-PVC), acrylic rubber (ACM), ethylene-acrylic rubber (AEM), chlorosulfonated polyethylene (CSM), etc., it exhibits excellent performance especially as a fuel hose for automobiles. In addition, the interlayer adhesion with the inner layer 1 formed by organic peroxide vulcanization is further improved. And these materials are used individually or in combination of 2 or more types. By the way, when the rubber outer layer 2 is formed using ECO or NBR-PVC, 1,8-diazabicyclo- (5,4,0) -undecene-7 is contained in the material for the rubber outer layer 2. It is preferable to contain (DBU) or a weak acid salt thereof because the interlayer adhesion with the inner layer 1 is more excellent.

  The rubber outer layer 2 may contain carbon black, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator, a processing aid, a white filler, a plasticizer, a softening agent, a receiving agent, if necessary. You may add an acid agent, a coloring agent, a scorch prevention agent, etc. suitably.

  2 and 3, examples of the reinforcing yarn forming the reinforcing yarn layer 3 provided between the layers include vinylon (polyvinyl alcohol) yarn, polyamide (nylon) yarn, aramid yarn, polyethylene terephthalate (PET) yarn. Etc.

  The method for braiding the reinforcing yarn is not particularly limited, and examples thereof include spiral knitting, knitting knitting, and blade knitting.

  In FIG. 2, the material for forming the outermost layer 4 provided on the outer periphery of the reinforcing yarn layer 3 is not particularly limited, but a rubber composition similar to that of the rubber outer layer 2 is usually used.

  Here, the fuel rubber hose shown in FIG. 1 can be manufactured as follows, for example. That is, first, the component materials (A) to (D) are prepared, and other component materials ((E), (F) component materials, etc.) are also prepared as necessary, and these are opened rolls or kneaders. A material composition for the inner layer 1 is prepared by kneading using a closed mixer such as the above. Moreover, the material composition for rubber outer layers 2 is also prepared by using the appropriate material and the same method. Next, after extruding the material composition for the inner layer 1 into a cylindrical shape, the material composition for the rubber outer layer 2 is directly applied without applying an adhesive to the surface (without an adhesive). A fuel-based rubber hose in which the outer layer 2 made of rubber is formed on the outer peripheral surface of the inner layer 1 can be obtained by extrusion molding on the material composition for the inner layer 1 and vulcanizing these layers. The above layers may be formed by coextrusion molding.

  The fuel rubber hose of the present invention shown in FIG. 3 can be manufactured, for example, as follows. That is, a composition for each layer is prepared by the same method as described above, and the material composition for the inner layer 1 is extruded into a cylindrical shape, and then a reinforcing thread is braided into a blade shape on the surface. Next, the reinforcing yarn layer 3 is formed on the outer peripheral surface of the inner layer 1 by extruding the rubber outer layer 2 material composition on the outer peripheral surface of the reinforcing yarn and vulcanizing these layers. A fuel rubber hose in which the rubber outer layer 2 is formed on the outer peripheral surface of the thread layer 3 can be obtained. The hose shown in FIG. 2 has a reinforcing yarn layer 3 formed on the outer periphery of the hose shown in FIG. 1 in the same manner as described above, and a rubber composition for forming the outermost layer 4 on the outer peripheral surface of the reinforcing yarn layer 3. It can be manufactured by extruding the product.

  In the fuel-based rubber hose of the present invention thus obtained, the inner diameter of the hose is preferably in the range of 2 to 30 mm, particularly preferably in the range of 5 to 25 mm. The thickness of the inner layer 1 is preferably in the range of 0.05 to 10 mm, particularly preferably in the range of 0.1 to 5 mm, and the thickness of the rubber outer layer 2 is preferably in the range of 0.05 to 10 mm. Especially preferably, it exists in the range of 0.1-5 mm.

  The fuel-based rubber hose of the present invention is not limited to the two-layer structure as shown in FIG. 1, and any configuration is acceptable as long as it has a laminated structure of the inner layer 1 and the rubber outer layer 2. It doesn't matter. Therefore, for example, the rubber outer layer 2 in FIG. 1 may be composed of two or more layers, each of which is made of different rubber. That is, a different rubber layer may be provided outside the rubber outer layer 2. Moreover, you may comprise a reinforcing thread layer as needed.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

  First, prior to the examples and comparative examples, the following materials were prepared.

[FKM polymer (component A)]
Daiel G901 (Iodine-containing fluororubber with a fluorine content of 71% by mass), manufactured by Daikin Industries, Ltd.

〔Carbon black〕
Seast S, manufactured by Tokai Carbon

[MgO (E component)]
Kyowa Mug # 150, manufactured by Kyowa Chemical Industry Co., Ltd.

[Organic peroxide cross-linking agent (component B)]
Perhexa 25B-40 [2,5-dimethyl-2,5-di (t-butylperoxy) hexane], manufactured by NOF Corporation

[Co-crosslinking agent (i) (C component)]
Thaik (triallyl isocyanurate), manufactured by Nippon Kasei Co., Ltd.

[Co-crosslinking agent (ii) (component D)]
Balnock GM (p-benzoquinone dioxime compound), manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

[Scorch inhibitor (F component)]
Noxeller TRA (dipentamethylene thiuram tetrasulfide), manufactured by Ouchi Shinsei Chemical Co., Ltd.

[Examples 1 to 20, Comparative Examples 1 to 10]
First, the above-prepared component materials are blended in the proportions shown in Table 1 below, and are kneaded using a closed mixer such as an open roll or a kneader to produce an inner layer material (a material composition for a fluororubber layer). A) to f were prepared.

  In addition, as shown below, outer layer materials (ECO layer material composition, NBR-PVC layer material composition, ACM layer material composition, AEM layer material composition, and CSM layer material composition) are prepared. did.

[Preparation of ECO layer material composition]
100 parts of ECO polymer (Zeklon 2000, manufactured by Nippon Zeon Co., Ltd.), 50 parts of carbon black (Shiest SO, manufactured by Tokai Carbon Co., Ltd.), 5 parts of plasticizer (Adekasizer RS107, manufactured by Asahi Denka Kogyo Co., Ltd.), and anti-aging agent 1 part (NOCRACK NBC, manufactured by Ouchi Shinsei Chemical Co., Ltd.), 3 parts processing aid (Emaster 510P, manufactured by Riken Vitamin Co.), 1 part DBU naphthoate (DA500, manufactured by Daiso Corporation), and acid receiving 1 part of an agent (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.), 1 part of a vulcanizing agent (Sunceller 22C, manufactured by Sanshin Chemical Co., Ltd.), and a kneading accelerator (Noctizer SS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 2 parts and 0.1 part of a vulcanizing agent (Sulfax T-10, manufactured by Karuizawa Smelter Co., Ltd.) are kneaded using an open type mixer such as an open roll or a kneader to produce an outer layer material (ECO layer). Material Composition) was prepared.

[Preparation of material composition for NBR-PVC layer]
100 parts of NBR-PVC polymer (Nipol 1203JN, manufactured by Nippon Zeon Co., Ltd.), 1 part of processing aid (Lunac S30, manufactured by Kao Corporation), 10 parts of crosslinking aid (2 types of zinc oxide, manufactured by Mitsui Kinzoku Mining Co., Ltd.) , 1 part of an anti-aging agent (Nonflex RD, manufactured by Seiko Chemical Co., Ltd.), 1 part of an anti-aging agent (Ozonon 3C, manufactured by Seiko Chemical Co., Ltd.), 40 parts of carbon black (Seast SO, manufactured by Tokai Carbon Co., Ltd.), DBU 2 parts of naphthoate (DA500, manufactured by Daiso Corporation), 15 parts of plasticizer (Adekasizer RS107, manufactured by Asahi Denka Kogyo Co., Ltd.), 1 part of vulcanizing agent (Sulfax T-10, manufactured by Karuizawa Smelter) And 1.5 parts of vulcanization accelerator (Noxeller TT, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.5 parts of vulcanization accelerator (Noxeller CZ, manufactured by Ouchi New Chemical Co., Ltd.), open roll or kneader, etc. Sealed type By kneading using a machine, the outer layer material (NBR-PVC layer material composition) was prepared.

[Preparation of ACM layer material composition]
100 parts of ACM polymer (Nipol AR31, manufactured by Nippon Zeon), 1 part of processing aid (Lunac S30, manufactured by Kao Corporation), 65 parts of carbon black (Seast SO, manufactured by Tokai Carbon Co., Ltd.), plasticizer (Adekasizer) RS735, manufactured by Asahi Denka Kogyo Co., Ltd.), anti-aging agent (Nauguard 445, Crompton Co., Ltd.) 2 parts, and vulcanizing agent (Barnock AB, Ouchi Shinsei Chemical Co., Ltd.) 1.5 parts, open roll Alternatively, an outer layer material (ACM layer material composition) was prepared by kneading using a closed mixer such as a kneader.

[Preparation of AEM layer material composition]
100 parts of AEM polymer (VAMAC GLS, manufactured by DuPont), 2 parts of processing aid (Lunac S30, manufactured by Kao Corporation), 60 parts of carbon black (Seast SO, manufactured by Tokai Carbon Co., Ltd.), and anti-aging agent (Naugard 445) 2 parts of Crompton), 0.5 parts of processing aid (Armin 18D, Lion Akzo), 4 parts of processing aid (Phosphanol RL210, Toho Chemical Industries), and vulcanizing agent Kneading 1.5 parts (Diac # 1, DuPont) and 4 parts vulcanization aid (Noxeller DT, Ouchi Shinsei Chemical) using a closed mixer such as an open roll or a kneader. Thus, an outer layer material (AEM layer material composition) was prepared.

[Preparation of CSM layer material composition]
100 parts of CSM polymer (TOSO TS-530, manufactured by Tosoh Corporation), 5 parts of acid acceptor (Starmag CX150, manufactured by Kamijima Chemical Co., Ltd.), 0.5 part of processing aid (Lunac S30, manufactured by Kao Corporation), 1 part of anti-aging agent (NOCRACK NBC, manufactured by Ouchi Shinsei Chemical Co., Ltd.), 30 parts of carbon black (Seast S, manufactured by Tokai Carbon Co., Ltd.), 60 parts of filler (Shiraka Hana CC, manufactured by Shiroishi Kogyo Co., Ltd.) (Diana Process NM300, manufactured by Idemitsu Kosan Co., Ltd.) 15 parts, vulcanization accelerator (Neuiser P, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 5 parts, vulcanizing agent (Noxeller TRA, manufactured by Ouchi Shinsei Chemical Co., Ltd.) The outer layer material (CSM layer material composition) is kneaded with 1 part of a vulcanization accelerator (Noxeller DM, manufactured by Ouchi Shinsei Chemical Co., Ltd.) using a closed mixer such as an open roll or a kneader. Preparation did.

[Production of hose]
Inner layer materials (fluorine rubber layer material composition) a to f and outer layer materials (ECO layer material composition, NBR-PVC layer material composition, ACM layer material composition, AEM layer material composition and CSM) A fuel system rubber hose was produced using the layer material composition) in combinations shown in Tables 2 to 6 below. That is, after the inner layer material is extruded into a cylindrical shape, the outer layer material is directly extruded without applying an adhesive to the surface (without an adhesive), and each of these layers is steam vulcanized (160 ° C. X45 minutes) to obtain a fuel rubber hose having a two-layer structure in which the outer layer is formed on the outer peripheral surface of the inner layer (see FIG. 1). The fuel rubber hose was prepared so that the inner layer had a thickness of 1.5 mm, the outer layer had a thickness of 1.5 mm, and the hose inner diameter was 10 mm.

  Using the fuel rubber hoses thus obtained, various properties were measured and evaluated according to the following methods. These results are shown in Tables 2 to 6 below.

[Interlayer adhesion]
A test piece having a thickness of 3 mm (inner layer thickness of 1.5 mm, outer layer thickness of 1.5 mm) and width of 25.4 mm was cut out from each hose, and the inner layer (fluororubber layer) of the test piece was removed from a tensile tester (JIS B). 7721), and peeled off at a speed of 50 mm per minute, and the interlayer adhesion (N / mm) at that time was measured. The interlayer adhesion required for the present invention is 2.0 N / mm or more.

[Crack propagation (solvent cracking)]
A notch scratch is made in the center of a JIS No. 1 dumbbell cut out from the inner layer of each hose, this dumbbell is stretched by 50%, immersed in 40 ° C. Fuel C (ethanol 10%), and the time (min) ) Was measured, and crack progressability (solvent crack property) was evaluated.

(Tensile permanent set)
A JIS No. 1 dumbbell cut out from the inner layer of each hose was stretched by 50% (distance between the marked lines after stretching was 60 mm, original distance between the marked lines was 40 mm), and was subjected to dry heat aging at 150 ° C. for 72 hours. Thereafter, the extension was released, the distance between marked lines X (mm) after cooling at room temperature for 30 minutes was measured, and the rate of change was calculated according to the following formula (A).

  From the above results, the products of all the examples obtained excellent results in interlayer adhesion and crack propagation (solvent crack property). Furthermore, good results were obtained in the tensile set of the inner layer.

  On the other hand, Comparative Examples 1, 3, 5, 7 and 9 did not use the co-crosslinking agent (ii) (p-quinonedioxime compound) in the inner layer material, and the crack progressability (solvent crack property). It turns out that it is inferior to evaluation of. It can be seen that Comparative Examples 2, 4, 6, 8, and 10 do not use the co-crosslinking agent (i) (triallyl isocyanurate) as the inner layer material, and are inferior in evaluation of interlayer adhesion and tensile permanent strain.

  The fuel rubber hose of the present invention is used for transportation of fuels such as automobiles (gasoline, alcohol-mixed gasoline (gasohol), light oil, FAME-mixed light oil, GTL, alcohol, hydrogen, LPG, CNG, etc.). Excellent performance as a heat resistant fuel hose for an injection system (new diesel engine system). In addition, it can also be used as a hose for a diesel particulate filter (DPF) system.

It is a block diagram which shows an example of the fuel type | system | group rubber hose of this invention. It is a block diagram which shows the other example of the fuel type | system | group rubber hose of this invention. It is a block diagram which shows the other example of the fuel type | system | group rubber hose of this invention.

Explanation of symbols

1 Inner layer 2 Rubber outer layer

Claims (5)

A fuel-based rubber hose comprising a tubular inner layer and a rubber outer layer provided in contact with the outer peripheral surface, wherein the inner layer uses a rubber composition having the following (A) to (D) as essential components A fuel rubber hose characterized by being formed.
(A) Iodine-containing fluororubber.
(B) Organic peroxide crosslinking agent.
(C) Triallyl isocyanurate.
(D) p-quinone dioxime compound. The fuel-based rubber hose according to claim 1, wherein the inner layer is formed using a rubber composition containing the following (E) component as an acid acceptor together with the essential components (A) to (D).
(E) Magnesium oxide. The fuel-based rubber hose according to claim 1 or 2, wherein the inner layer is formed by using a rubber composition containing the following component (F) as a scorch inhibitor together with the essential components (A) to (D). .
(F) Dipentamethylene thiuram tetrasulfide.   The rubber outer layer is composed of epichlorohydrin-ethylene oxide copolymer rubber (ECO), acrylonitrile-butadiene rubber and polyvinyl chloride blend rubber (NBR-PVC), acrylic rubber (ACM), ethylene-acrylic rubber (AEM) and chloro. The fuel rubber hose according to any one of claims 1 to 3, wherein the fuel rubber hose is formed using at least one selected from the group consisting of sulfonated polyethylene (CSM).   In the fuel-based rubber hose in which the rubber outer layer is formed using ECO or NBR-PVC, 1,8-diazabicyclo- (5,4,0) -undecene-7 ( DBU) or its weak acid salt, The fuel type | system | group rubber hose as described in any one of Claims 1-4.

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