TWI259882B - Rubber hose and method of manufacture - Google Patents

Abstract

The present invention relates to a rubber hose that is formed by laminating an outer rubber layer on the outer periphery of an inner rubber layer by an extrusion method wherein the inner rubber layer is formed of fluoro-rubber layer 2, and the outer layer is formed of a reinforced yarn knitted-in silicone rubber layer 1 of knitting reinforced yarn inside, an intermediate rubber layer including an adhesive component to be adhered to the fluoro-rubber layer in arranged between the fluoro-rubber layer 2 and the reinforced yarn knitted-in silicone rubber layer 1 and the intermediate rubber layer is formed of the intermediate silicone rubber layer 3 having hardness lower than the reinforced yarn knitted-in silicone rubber layer, and a method of manufacture thereof. In addition, the present invention relates to a rubber hose that is formed by laminating an outer rubber layer on the outer periphery of an inner rubber layer by a winding method, wherein the inner rubber layer is formed of the fluoro-rubber layer 5, the outer rubber layer is formed of a reinforced cloth containing silicone rubber layer 4, an intermediate rubber layer including an adhesive component to be adhered to the fluoro-rubber layer 2 is arranged between the fluoro-rubber layer 5 and the reinforced cloth containing silicone rubber layer 4, and this intermediate rubber layer is formed of the intermediate silicone rubber layer 6 having hardness lower than the reinforced cloth 1 containing silicone rubber layer 4.

Description

1259882 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a rubber hose which can withstand oil resistance which allows a high-temperature gas to flow, and a method for producing the same. [Prior Art] As is conventionally, a rubber hose is connected between a turbine charger of an automatic vehicle and an intercooler, and a fan of a turbo charger is used to circulate the pressurized inhaled gas to the rubber. In the hose. Since the fan is driven by the exhaust gas of the engine, the temperature of the intake gas is made very high. Therefore, the rubber hose must have heat resistance against such high temperatures and vibration durability at high temperatures. For the material of a rubber hose which can withstand such a high temperature, ruthenium rubber has been conventionally used. However, the recent turbocharger has a higher pressing force, and therefore it is required to have a heat resistance of more than 200 °C. Moreover, with the introduction of the recent new short-term diesel vehicle exhaust restrictions, it is also necessary to install a vehicle exhaust regenerative device. Along with this, the rubber hose must also have oil resistance and gas permeability resistance to prevent the passage of automobile exhaust gas. Rubber hoses that are required to have such strict heat resistance and oil resistance are not sufficient for conventional rubber, so new materials are necessary. Therefore, the fluororubber which is excellent in heat resistance and oil resistance has been attracting attention, and attempts have been made to fabricate a laminated hose using fluororubber on the innermost portion of the gas hose (for example, Japanese Patent Laid-Open No. 2000) 1 1 3 3 1 5 2 幸 g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g It is quite difficult to obtain a hose that can withstand oil resistance and high-temperature vibration durability at a high temperature by combining the characteristics of each material. The focus of this technology is... 1) The method of obtaining the adhesion between the fluororubber and the ruthenium rubber which can withstand the chemical stability of each other even under the above-mentioned severe conditions. 2) The innermost fluororubber is because It is highly rigid and lacks softness. In particular, under the conditions of use of the scrambler charger hose, that is, at a high temperature of 180 to 200 ° C, the common disadvantage of becoming very fragile and easily damaged is due to the difficulty in material properties. What kind of structure is the problem. 3) Since the fluororubber is high in crystallinity, it is likely to cause a large leak of gas leaking from the joint portion of the hose at a low temperature which is poor in cold resistance. 4) Furthermore, fluororubber is a very expensive material, so it is important from an economic point of view how to form a thin fluororubber layer. In order to obtain a practical hose, it is necessary to have a method of collectively solving the problems of the above 1) to 4), but there is no description about this point in the above publication. In particular, although it is disclosed that the fluororubber and the ruthenium rubber are followed by the "use of ordinary vulcanization and subsequent bonding", when a special formulation is not added to the rubber blending, the ordinary vulcanization method is followed by the fluororubber. It is not feasible with enamel rubber. SUMMARY OF THE INVENTION A first object of the present invention is to provide a novel rubber hose and a method of manufacturing the same that can solve the above problems. -6 - (3) 1259882 Another object of the present invention is to provide a special intermediate rubber layer between the fluororubber layer and the ruthenium rubber layer of the outer layer, so that the low durability and low adhesion of the fluororubber layer can be obtained. Improved improved rubber hose. According to the first aspect of the present invention, the rubber hose in which the outer rubber layer is laminated on the outer periphery of the inner rubber layer by the extrusion method is characterized in that the inner rubber layer is a fluororubber layer and the outer rubber layer is formed. An reinforced rubber layer is woven into the reinforcing yarn in which the reinforcing yarn is woven, and an intermediate rubber layer containing an adhesive component with the fluororubber layer is disposed between the fluororubber layer and the reinforcing yarn woven into the enamel rubber layer, and the The intermediate rubber layer is an intermediate rubber layer having a lower hardness than the reinforcing yarn woven rubber layer and the innermost fluorine rubber layer. Further, in terms of resistance to an amine serving as an anti-aging agent and a rust preventive agent contained in engine oil, the fluororubber is a terpolymer (vinylidene fluoride, hexafluoropropylene, and tetrafluoropropene), Or a copolymer of tetrafluoroethylene and propylene is preferred. The rubber hose according to the first aspect described above is preferably produced according to the second manufacturing method. In other words, a method of manufacturing a rubber hose in which an intermediate kneading rubber layer having a lower hardness than a reinforcing yarn is woven into a rubber layer is disposed between the fluororubber layer and the outer peripheral reinforcing yarn woven rubber layer, The utility model is characterized in that: in a stacked state, a fluororubber layer, an intermediate yoke rubber, and a reinforcing yarn are woven into a lower layer of ruthenium rubber by a first extruder, and then supplied to a knitting machine, and the reinforcing yarn is woven into the reinforcing yarn by the knitting machine. After being placed on the outer periphery of the lower layer of the rubber, it is supplied to the second extruder, and the reinforcing yarn (4) 1259882 is woven into the upper layer of the woven rubber and laminated on the outer circumference of the woven reinforcing yarn by the second extruder. . According to the second aspect of the present invention, the rubber hose in which the outer rubber layer is laminated on the outer periphery of the inner rubber layer by the winding method is characterized in that the inner rubber layer is a fluororubber layer and the outer rubber layer is provided. The layer is a reinforcing rubber layer disposed between the fluororubber layer and the reinforcing rubber layer, and an intermediate rubber layer containing the adhesive component of the fluororubber layer is disposed, and the intermediate rubber layer is disposed. It is an intermediate rubber layer having a lower hardness than the above-mentioned fluororubber layer of the inner rubber layer and the inner layer. The rubber hose according to the second aspect described above is preferably manufactured by the second method. In other words, a winding method of the intermediate rubber layer having a lower hardness than the fluororubber layer in which the ruthenium rubber layer and the inner layer are reinforced is disposed between the fluororubber layer and the outer periphery thereof. A method for producing a rubber hose, comprising: forming a fluororubber layer sheet by a calender roll, and pressing and bonding the intermediate ruthenium rubber to form a laminated sheet of a fluororubber layer sheet and an intermediate ruthenium rubber layer sheet, and laminating the sheet After the sheet is wound on a metal mandrel of a predetermined shape, the hose is prepared by winding a pre-formed reinforcing top sheet of the rubber. At this time, the middle 矽 rubber has a material hardness that is softer than the hardness of the reinforced rubber. Further, the top sheet, that is, the reinforced rubber layer (hereinafter referred to as a ruthenium rubber layer) sheet, is inserted into the ruthenium rubber, such as an aromatic polyamide or the like. However, it is also possible to After the kneading rubber is kneaded by a roll to achieve thermal plasticization, a -8-(5) 1259882 strong cloth is supplied, and a calender roll is used to press the ruthenium rubber on both sides or a single surface thereof. In the method for producing a rubber hose according to the second aspect of the present invention, "the ruthenium rubber is extremely soft, and it is extremely difficult to form a film system having a thickness of about 0·1 to 0.3 mm. However, since the laminated sheets of the fluororubber layer sheet and the intermediate ruthenium rubber sheet are continuously formed by the calender rolls, the hardness of the unsulphurized fluororubber can be used to complement the softness of the 而 rubber to improve workability and molding. Sex. Along with this point, the thickness of the fluororubber layer sheet can be made thin, and at this time, since the soft enamel rubber is pressed in the state of thermal softening, the two sheets can be pressed together, thereby improving mutual The adhesion and the advantages of the air incorporated therein can be excluded. According to this method, since the fluororubber layer sheet can be formed into an extremely thin state of 〇 1 mm, it is advantageous in terms of cost as compared with extrusion molding. The fluororubber is hard and lacks flexibility, especially when a significant vibration is applied under high temperature conditions, and the disadvantage of being easily broken under stress concentration is as described above. For this reason, when the fluororubber layer and the reinforcing yarn are woven (or reinforced) into the 矽 rubber layer, a fluororubber layer which is woven and woven into the 矽 rubber layer constituting the reinforcing yarn (or reinforcingly disposed) is disposed. When the intermediate rubber layer composed of ruthenium rubber having a lower hardness acts as a cushioning material, the stress applied to the fluororubber layer of the inner layer can be dispersed. Further, when it is compared with the case where the fluororubber and the ruthenium rubber are directly adhered to each other, it is soft and the adhesion of the same material is followed, so that a better adhesion and adhesion can be obtained. The subsequent component is because only -9 - (6) 1259882 is blended in the middle rubber layer, so that the amount of the subsequent components can be reduced to achieve economic benefits. In addition, since the fluororubber is also inferior in cold resistance, when it is inserted into the opposite pipe, the sealing property in the cold is reduced, but by laminating the intermediate ruthenium rubber layer excellent in cold resistance, Can improve the sealing. [Embodiment] (First Embodiment) A rubber hose according to a first embodiment of the present invention will be described with reference to Figs. 1 to 3 . Basically, for a rubber hose in which an outer rubber layer is laminated on the outer periphery of the inner rubber layer by an extrusion method, the inner rubber layer is a fluororubber layer 2, and the outer rubber layer is a reinforced yarn in which the reinforced reinforcing yarn is woven.矽 rubber layer 1. Between the fluororubber layer 2 and the reinforcing yarn woven rubber layer 1, an intermediate rubber layer 3 containing an adhesive component with the fluororubber layer 2 is disposed, and the intermediate rubber layer 3 is woven with a reinforcing yarn. Layer 1 and fluororubber layer 2 have a lower hardness intermediate rubber layer. The basic items of the rubber hose according to the first embodiment of the present invention are as described above. However, when the following additional means are clarified, the function and characteristics can be further improved. Therefore, reference is made to FIG. 1 below. 2A and 2B are explained. Such a rubber hose is manufactured by extrusion molding as described above, but when the point is slightly supplemented, it is pushed out by a general extrusion method. In other words, in order to ensure the accuracy of the inner diameter and the anti-deformation of the unsulfurized rubber-10-(7) 1259882 hose, a core mandrel (not shown) is used, and the core mandrel is supplied to the actual The upper one is one of the first extruders 10 (only one), and the first extruder 1 is attached to the outer circumference to make the fluororubber layer 2 and the middle rubber. The layer 3 and the reinforcing yarn are woven into the lower layer of the rubber layer 1 a and are extruded in a stacked state. After the laminated body pushed out by the first extruder 1 is supplied to the knitting machine 1 1, the knitting machine 1 1 woven a heat-resistant fiber such as an aromatic polyamide fiber to the outermost layer of the laminate, that is, the reinforcing yarn is woven. The outer circumference of the rubber lower layer 1 a. Further, the reinforcing yarn weaving method according to the knitting machine 1 is also the same as the conventional one, such as an interlacing method, a spiral weave method, and a knitting method. On the outer circumference of the reinforcing yarn 1b woven by the reinforcing yarn, the enamel rubber layer 1c is laminated and then pushed out. In this case, the woven fabric of the reinforcing yarn and the side or both sides of the enamel rubber layer are required to be formed into a suitable multi-layer shape in accordance with the requirements required for pressure resistance and the like. In this way, the continuously extruded laminate is cut at a predetermined length and the core mandrel is pulled out, and then the vulcanization mandrel is inserted, and then a predetermined sulfurization treatment or the like is applied to obtain a desired one. product. However, although the organic decane coupling agent as an adhesive is applied to the outer periphery of the fluororubber layer 2, this case is as shown in Fig. 2B, and if the fluororubber layer 2 using the first extruder 1 is applied, And the intermediate rubber layer 3, and the reinforcing yarn woven into the lower layer 1a of the rubber, and are divided into two upper and lower extrusions. The first extruder i 〇a is the fluororubber layer, and secondly, the organic decane coupling agent. The coater 1 3 is coated with an organic decane coupling agent, and after passing through the dryer 14 , the intermediate rubber layer 3 and the reinforcing yarn are woven into the lower rubber layer 1 a -11 by the lower first extruder 10 b. (8) 1259882 The operation of the extrusion is better. For the rubber hose manufactured by the above method, the thickness of the fluororubber layer which is required to have heat resistance and oil resistance is preferably 0.2 to 1.5 mm when the durability and economy are considered. Here, the lower limit of the thickness of 2 mm is the limit of the use of the extrusion, and may be 0. 1 mm if possible. Although the fluororubber is hard and lacks flexibility, it also has the disadvantage of being weak at high temperatures. As described above, under the condition of vibration at a high temperature of 200 ° C and vibration, the tensile strength of stretching is lowered and there is a possibility of destruction. In addition, when the fluororubber layer 2 is thinner than necessary, the rigidity of the rubber hose is increased by hardening at a low temperature, and thus the original performance such as sealing property and vibration absorbing property cannot be exhibited. In view of this, the thickness is quite important, so the above range is appropriate. Table 1 shows the results of the vibration endurance test at 180 ° C (with or without cracks) after changing the thickness of each of the fluororubber layers 2 'but any fluororubber is the same, when the thickness exceeds 1.5 mm, Poor quality. In the table, 〇 indicates that no crack is generated, △ indicates that micro cracks are generated (depth is 0 · 5 mm or less), and χ indicates that large cracks are generated (depth is more than 0 · 5 mm). 1259882 (9)

Thickness (mm) 0.2 0.5 1 .0 1.2 1 .5 2.0 2.5 Fluororubber A 〇〇〇〇〇XX Fluororubber B 〇〇〇〇〇Δ X Fluororubber C 〇〇〇〇〇Δ X Fluororubber A: Asahi Glass Co., Ltd. Hardness (JIS A) 7 〇Fluororubber B: Hardness (JIS A) manufactured by Sumitomo 3M Co., Ltd. 7 0 Fluorine rubber C: Hardness made by Daikin Co., Ltd. (JIS A ) 7 0 Also, for the above fluororubber, 'use 3 Any one of a copolymer (vinylidene fluoride, hexafluoropropyl, and tetrafluoropropene: fluororubber 5 and [)' and a copolymer of tetrafluoroethylene and propylene (fluororubber A). The intermediate rubber layer 3 disposed between the fluororubber layer 2 and the reinforcing yarn woven rubber layer 1 (hereinafter referred to as the ruthenium rubber layer 1) and serving as a cushioning material for both of them has a yoke rubber layer 1 and The hardness of the fluororubber layer 2 is a good condition with a low hardness. Specifically, it is preferable to achieve a lower J I S A hardness of 1 〇 to 30. Further, the thickness of the intermediate rubber layer 3 is suitably 0.33 mm. The intermediate enamel rubber layer 3 bears the stress of the fluororubber layer 2, and although it must be 〇·3 halo or more, it is not required to be too thick, and it is suitably 2 mm or less. When the thickness is exceeded, the lower portion of the tightening tape or the like which is fitted and attached to the outer periphery of the silicone rubber layer 1 may cause fatigue and is not suitable. Further, in the intermediate rubber layer 3, -13-(10) 1259882 has a disadvantage that the price is increased when the thickness is increased because the adhesive composition is blended. The effect can be achieved by blending the aromatic polyamide short fibers on the fluororubber layer 2. When the fluororubber is heated, its strength is lowered, and if such heat-resistant short fibers are blended, the strength can be prevented from being lowered. Moreover, these short fibers can exert anchoring effects and can also improve adhesion. The blending amount of the aromatic polyamine short fibers is suitably 5 to 40 parts by weight (hereinafter, expressed by 5 to 40 PHR) based on 100 parts of the raw material polymerization. When the range is exceeded/not full, the above function is lowered. In the case of aromatic polyamine short fibers, aromatic polyaromatic polyamides such as polyparaxyl phthalamide and poly-phenylenediamine meta-xylyleneamine are used. When the eucalyptus oil is blended on the fluororubber layer 2, the elongation property can be remarkably improved to improve the durability. For the eucalyptus oil, polymethyl hydrazine (1), polymethylphenyl hydrazine (2), etc. can be used, and 0 5 to 10 PHR is suitable. When it is less than 〇·5, the effect will be low. When it exceeds 10 PHR, it will cause difficulty in subsequent operations. Therefore, it is usually 1 to 3 PHR. In Table 2 below, the relationship between the blending amount and the elongation index is shown. Table 2

Unblended fluororubber Μ ) 3 P _( 2 ) 3 , PH^R elongation index 10 0 13 0 15 0 (11) 1259882 The addition of magnesium oxide to the intermediate rubber layer 3 can also improve the adhesion. Be applicable. In general, an amine sulfur addition type or a polyol sulfur addition type fluororubber is blended with magnesium oxide as an acid acceptor, but when the magnesium oxide is also blended on the intermediate side rubber layer 3 on the side to be joined, Then the power is improved. The amount of magnesium oxide blended is suitably 2 to 15 PHR. When it is less than 2 P H R , the effect is lowered, and when it exceeds 15 P H R , it is not suitable because the intermediate ruthenium rubber layer 3 is hardened and its durability is lowered. Table 3 below shows the relationship between the amount of magnesium oxide blended and the adhesion. Table 3 Shuttle quantity (PHR) 0 2_1 0 15 Ρ. 0 Subsequent X △ 〇〇 hardening damage X: interface damage △: part of interface damage 〇: material damage makes fluororubber layer 2 peroxide peroxide type In the case, when the isodecyl cyanurate is blended in the intermediate ruthenium rubber layer 3, the adhesion strength can be clearly improved. In terms of the blending amount, it is appropriate to use 1 to 15 PHR. When the PHR is less than 1 PHR, the effect is lowered. When it exceeds 15 P H R, premature vulcanization and viscosity increase are not applicable. In the following Table 4, the relationship between the blending amount and the adhesion according to the type of the fluororubber is shown. Among them, the type and evaluation symbol of the fluororubber are the same as those in the above Table 3 (the same applies to the case of Table 5). -15· 4 (12) 1259882

Unblended, 1 5 10 15 2 0 X Δ 〇 〇 硬化 hardening X 〇 〇 〇 硬化 hardening blending amount (P H R )

Fluororubber Β Fluororubber C Further, when the intermediate ruthenium rubber layer 3 is blended with the organic decane coupling agent, the adhesion can be clearly improved. In the case of the organic decane coupling agent, the amine group having an organic functional group and the epoxy group are hydrazine. The blending amount is suitably 〇 5 to 15 PHR. When the temperature is less than 0.5 Phr, the effect is reduced. When it exceeds 15 PH R, the pre-vulcanization is not applicable. In Table 5 below, the relationship between the amount of amino decane blended according to the type of fluororubber and the adhesion is shown.

The blending amount (P HR) is not blended 0. 2 0 . 5 2 5 10 15 Fluororubber BXX Δ 〇〇〇 Hardened fluororubber CX 〇〇〇〇〇 Hardening On the one hand, when the rubber hose is placed in the so-called 2 When the temperature is applied at a high temperature of 0 0 t and the vibration is applied thereto, the fluororubber layer 2 and the opposite tube (not shown) are thermally fixed, and it is difficult to disassemble. In order to prevent this, the release agent can be applied to the inner circumference of the -16-(13) 1259882 of the fluororubber layer 2 of the fitting portion. When the release agent is applied, since the dynamic friction coefficient can be reduced, the fixation can be controlled. Although there are various types of release agents, the release hardening of the lanthanide is high and suitable. However, this type of rubber hose is usually subjected to post-sulfurization at a temperature of 200 ° C for 5 hours in order to fully exert the required function, so the release agent is used before this operation. It is coated by bristles or the like, and is then cemented by post-sulfurization. In the following Table 6, the use of the cement type crepe release agent HS-1 (manufactured by Toshiba Corporation) was carried out, and the mold release treatment and the non-user's dismountability (fixing adhesion resistance) were compared, but the release agent was applied. The result is a greatly improved dynamic friction coefficient, which can be disassembled by hand. Table 6 Resistance to fixed joints Motorized ages uncoated X 1 Coating 〇0. 3 X: Fixing is then quite firm, and disengagement must be used for disassembly: as long as the hand can be used to remove the condition: for the opposite direction The pipe system was selected from aluminum, and after 168 hours of belt-type tightening test under 20 〇t:, the fixed adhesion was reviewed. Furthermore, for the above-mentioned crack countermeasure, the symbol of the fluororubber layer -17-(14) 1259882 in the fitting portion is used for the end portion to be stretched in the twisting direction in the twisting direction, and it is possible to prevent the circumferential direction from being convex. The number of the edge 7 can be reduced because of the effect. The plurality of convex rubber hoses of the fitting portion, although also provided by the provision of the male molding agent, can be tightly tightened under the torque of the belt, that is, even if it is not made on the inner circumference of 2 When the core tube is in the upward direction, the flange 7 is formed. Moreover, the closing property is not present, and the contact area which can be improved is as follows: the protruding height is 0. When the flange is tightened, the nature of the above-mentioned de-control crack is further set to 1 5 N - m Occurs, but 1 Ο N — m either causes solidification and the flange is effective. The shaft is made of a fluororubber layer 2, and the flange 7 of the flange 7 is affected by this effect. Furthermore, it is also possible to achieve the application of a molding agent using a .5 mm, rubber hose or crack, and this further improvement of N - m, degree, by application is even the ratio of the tightening condition The splicer also has (refer to the third point, this point can be taken. When the length of the hose is extended to be formed when it is formed, the structure is attached to the rubber hose with a width of 3 mm. And there is no flange investigation result. The effect is, however, when the coating is decontaminated. In addition, although this is more strict with the above-mentioned various types, the problem is remarkable, and the effect is 7) that the rubber has a flange shape on the circumference, At this time, when the burst crack is generated, the edge 7 is made on the inner circumference of the opposite tube when the density is plural, and the edge 7 is investigated by the tightening, and the tightening torque of the fixed joint can be made ^ That is, it can suppress the crack is a severe crack occurrence (15) 1259882

Flange release agent coating crack hair extension fixed rubber hose (1) Μ 〆V,, ίκ Tiny occurrence X rubber hose (2) Sister > V \\ 〇 rubber hose (3) Yes Μ j \ \\ ◎ The X and 〇 in the comments on the fixed adhesion are the same as the above, and the ◎ means a simple disassembly state by hand. In order to make the fluororubber layer 2 and the intermediate ruthenium rubber layer 3 follow-up, it is possible to apply the above-mentioned other or use the organic ruthenium coupling agent as a main component to the fluororubber layer. On the method. The coating system is divided into the upper first extruder 1 by the extrusion of the fluororubber layer 2, the intermediate rubber layer 3, and the lower rubber layer 1a by the first extruder 10 as shown in Fig. 2B. The extrusion of the fluororubber layer 2 of 〇a, the application of the organic decane coupling agent by the organic decane coupling agent coater 13 and the use of the intermediate ruthenium rubber layer 3 and the ruthenium rubber lower layer 1a of the first extruder 1b below The extruding can thus be done automatically during the extrusion process. According to this, the adhesion of the fluororubber layer 2 and the intermediate ruthenium rubber layer 3 can be improved. For the organic binder, Cheml ockS — 2, S—1〇Α,

Me g amu 3 2 9 0 — 1 and so on. Since these adhesives are alcohol solutions, it is preferred that the coater be sprayed. -19- (16) 1259882 [Example 1]

A rubber hose (Y) in which the fluororubber B is the fluororubber layer 2, and an intermediate sand rubber layer 3 is disposed between the ruthenium rubber layer 2 and the ruthenium rubber layer 1 is manufactured, and the rubber of the 'sand rubber rubber layer 1 is omitted. Hose (Z). This manufacturing system is a method of forming a fluororubber layer 2, an intermediate ruthenium rubber layer 3, and a ruthenium rubber layer 1 by the method of the first extruder ι, the braiding machine 1 1 and the second extruder 1 2 as shown in Fig. 2A. A laminate of (JISA hardness 70). The rubber hose (Z) omits the intermediate rubber layer. In this case, the thickness of the fluororubber layer is set to 〇·3 mm, and the intermediate ruthenium rubber layer 3 is JISA hardness 50 and contains magnesium oxide 5 PHR, triallyl cyanurate 10 PHR' and thickness Set 疋 to 1 · 〇 mm. After the rubber hose is cut to a predetermined length, the core mandrel is pulled out, and then a vulcanization mandrel having an outer diameter of 50 mm and a wrinkle is attached, and the entire ring is bundled by heat shrinkable tape, and then placed. In a steam tank, it was shaped by adding sulfur for 30 minutes at a temperature of 165 °. After the vulcanization is completed, the tape is unwound, and in order to achieve proper physical properties, it is placed again in a constant temperature bath, and the vulcanization is performed twice at 5 o C ° C for 5 hours. When the rubber hoses of the above-mentioned (Y) and (Z) which are thus twisted and tightened under a torque of 5 N - m are subjected to the heat resistance endurance test at 18 ° C, (Y) The rubber hose is not abnormal, and the rubber hose of (Z) is cracked on the fluororubber layer 2 under the tightening belt, so that the effectiveness of the intermediate rubber layer 3 can be determined. As described above, in the rubber hose in which the fluororubber layer 2 and the ruthenium rubber layer 1 are laminated, between the fluororubber layer 2 and the ruthenium rubber layer 1, the ruthenium rubber constituting the ruthenium rubber layer 1 and the fluororubber are disposed. When the fluororubber of the layer 2 has a lower hardness of -20-(17) 1259882, the intermediate ruthenium rubber layer 3 composed of ruthenium rubber acts as a cushioning material and can be dispersedly applied to the fluororubber layer 2. The stress is increased, and since the intermediate rubber layer 3 is soft, the adhesion to the fluororubber can be improved. Further, since the adhesive agent is only blended in the intermediate rubber layer 3, it is economical to reduce the amount of the adhesive. (Second Embodiment) A rubber hose according to a second embodiment of the present invention will be described with reference to Figs. 3 to 7 . First, in the fourth embodiment to the seventh embodiment, the rubber hose according to the second embodiment is a rubber hose in which the outer rubber layer is laminated on the outer periphery of the inner rubber layer by a winding method to form an inner rubber layer. It is a fluororubber layer 5, and the outer rubber layer is reinforced and disposed in the ruthenium rubber layer 4, and between the fluororubber layer 5 and the reinforced rubber layer 4 is disposed, and the composition corresponding to the fluororubber layer 5 is disposed. The intermediate rubber layer 6 is formed such that the intermediate rubber layer 6 is made of an intermediate rubber layer 6 having a lower hardness than the reinforcing rubber layer 4 and the fluororubber layer 5. In the second embodiment of the present invention, the basic matters are the same as those described above, but when the following additional means are further described, the functions and characteristics can be improved. The details are not greatly different from those of the first embodiment described above, and the case is as follows. In other words, the thickness of the fluororubber layer 5 which is required to have heat resistance and oil resistance is preferably from 0. 1 to 0.5 mm in consideration of durability and economy. Although the fluororubber is hard and lacks flexibility, the -21 - (18) 1259882 has the disadvantage of being weak at high temperatures. As described above, at a high temperature of about 20 Torr, and under the condition of applying vibration, the tensile strength for stretching is lowered and there is a ruin. In order to solve this, the thickness thereof is quite important, and although the above range is appropriate, as described above, in the winding method, since the fluororubber layer 5 can be made thin by a calender roll, it is made to 0. 1~0 · 5 mm fluoro rubber layer 5 hose, so it is beneficial to the cost. The various experimental results (Tables 1 to 7) described above with respect to the first embodiment and their related descriptions are also the same in the second embodiment of the present invention. However, in order to surely form the fluororubber layer 5 and the intermediate ruthenium rubber layer 6, when a laminated sheet is formed by a calender roll, an organic binder containing a coupling agent as a main component is applied onto the outer periphery of the fluororubber sheet. The method and the like are the same as described above, and the adhesive is because it is an alcohol solution' so that it can be uniformly applied to the sheet of the fluororubber layer 5 by spraying. Further, at the time of the calender roll processing, as shown in Figs. 6 and 7, it is preferable to form an embossing on the outer peripheral surface of the fluororubber layer 5 which is the intermediate ruthenium rubber layer 6 side. This embossing can be carried out on the fluororubber layer 5, and it can be formed by usual embossing. As a result, the surface area can be increased and the adhesion between the fluororubber and the ruthenium rubber in the case of unsulphurization can be improved by the anchoring effect, and it is also expected that the adhesion force after the sulphurization becomes stronger. Further, the flange (the symbol 7 in Fig. 3) formed in the first embodiment may be formed of the same flange 7 as the fluororubber layer 5 of the second embodiment (see Fig. 3). The manufacturing method, action, and effect are the same as those in the first embodiment. -22- (19) 1259882 According to the embodiment of the second embodiment described above, the second embodiment and the third embodiment are described as follows. [Example 2] A rubber hose (Y) using the fluororubber B as the fluororubber layer 5' and the ruthenium rubber containing the JIS A hardness 40 of the amino decane 2PHR as the intermediate zea rubber layer 6 was tested and omitted. This intermediate rubber layer 6 is only followed by the performance of the rubber hose (Z) of the rubber layer. The rubber hose is formed as shown in Fig. 5, and is made of a fluororubber sheet (symbol 20)' and the fluororubber layer 5 and the intermediate ruthenium rubber layer 6' are laminated by a calender roll, and the thickness of the fluororubber layer is 0. · 2 mm, the middle 矽 rubber layer 6 is 1 · 0 mm. Further, the top sheet of the enamel rubber layer is formed by applying a calender roll having a JIS A hardness of 65 to both sides of the meta-type aromatic polyamide fabric (symbol 2 1) by a calender roll, and forming a thickness of 1 · 5 mm laminated sheet. On the iron mandrel with an outer diameter of 85 mm and a corrugated iron, a laminated sheet of a sheet of the fluororubber layer 5 and a sheet of the intermediate rubber layer 6 is wound, and then wound into a top sheet of the enamel rubber layer to give a layer of 3 Shape (symbol 2 2 ) ' Thereafter, the entire ring was bundled with a shrinkable tape, placed in a steam can, and sulfurized at a temperature of 165 ° C for 30 minutes. After the completion of the vulcanization, the tape was unwound, and in order to obtain appropriate physical properties, it was placed in a hot air tank again, and the vulcanization was performed twice at 200 ° C for 5 hours. Using the rubber hoses of the above (Y) and (Z) thus obtained, a 1 80 t: endurance test was conducted, and the results were compared. According to the above results, the rubber hose of (γ) is not abnormal, and the rubber hose of (Z) is cracked on the fluororubber-23-(20) 1259882 下方 under the tightening belt, so the intermediate 矽 can be confirmed. The effectiveness of the rubber layer. [Example 3]

A rubber hose 1) in which the fluororubber C is a fluororubber layer 5 and a magnesia 7 P HR is blended on the JISA hardness of 50 作为 as the intermediate zea rubber layer 6 is carried out, and the blending is not oxidized. Performance test of magnesium rubber hose 2). In this case, the thickness of the fluororubber layer is set to 0. 2 mm, and the thickness of the intermediate ruthenium rubber layer is set to 0.5 mm. For the top sheet or hose of the ruthenium rubber layer, sulfur is added, and the forming system is used. The same method as the above [Example 2]. Using the rubber hoses of the above 1) and 2) produced as described above, the same test as above was carried out, and the results were compared. According to the above results, the rubber hose of 1) is not abnormal in the entire field, and the rubber hose of 2) is peeled off under the tightening belt and the fluororubber layer 5 at the end of the hose, so that it can be confirmed The effectiveness of magnesium oxide. [Example 4] In the same manner as in Example 2, a fluororubber layer of 0.2 mm in thickness <: (118 A hardness 60) was used as the fluororubber layer 5, and the basic compounding ratio was polymethyl hydrazine oil 3 PHR and Magnesium 10PHR hard material (JIS A hardness 45) is a middle 矽 rubber layer 6 with a thickness of 1.0 mm, and is wound and reinforced into a 矽 rubber (JIS A hardness 65, total thickness of 1.3 mm) Two kinds of hoses having three layers and no intermediate rubber layer 5 are provided. -24- (21) 1259882 Using this, put 50 grams of engine oil in the inner surface and perform the low-temperature seal endurance test (at -40t, internal pressure 0~250kpa), without intermediate rubber layer 5 The oil infiltration drip occurs from the end, while the intermediate rubber layer 5 has no leakage at all. Thereby, it is possible to use the intermediate rubber which is excellent in cold resistance and has flexibility to complement the low temperature property of the fluororubber, and to exhibit its excellent characteristics. In the case of the rubber hose in which the fluororubber layer 5 and the ruthenium rubber layer 4 are laminated according to the second embodiment, as in the case of the first embodiment, the fluororubber layer 5 and the ruthenium rubber layer 4 are used. An intermediate rubber layer 6 made of ruthenium rubber having a lower hardness than the ruthenium rubber and the fluororubber constituting the ruthenium rubber layer 4 is disposed, and the intermediate ruthenium rubber layer 6 is acted as a cushioning material, and can be dispersedly applied to fluorine. The stress on the rubber layer 5 can also be thinned. Further, since the intermediate rubber layer 6 improves the adhesion to the fluororubber layer 5, the adhesion of the adhesive is improved, and the adhesive is only required to be blended in the intermediate rubber layer 6, and therefore, It is economical to reduce the amount of the adhesive. [Brief Description of the Drawings] Fig. 1 is an explanatory view showing an embodiment of a rubber hose according to a first embodiment of the present invention. Fig. 2A is an explanatory view showing a suitable manufacturing method of the rubber hose shown in Fig. 1. Fig. 2B is an explanatory view showing another manufacturing method of the rubber hose shown in Fig. 1. -25- (22) 1259882 The third figure is m >>ννχ shows the rubber hose shown in Fig. 1 and the rubber hose of the second embodiment shown in Fig. 4 in the opposite tube Example of forming a flange on a fitting portion 〇 Fig. 4 is a view showing an embodiment of the rubber hose of the second embodiment of the present invention. Fig. 5 is a view showing the rubber shown in Fig. 4. Explanation of the suitable manufacturing method for the hose Ο Fig. 6 and Fig. 7 show an example of embossing on the rubber hose shown in Fig. 4. 〇 Symbols are simple explanation 1 Reinforced yarn woven into the rubber layer 1 a Reinforced yarn woven into 上 rubber upper layer 1 b reinforced yarn 1 c reinforced yarn woven into 矽 rubber lower layer 2 fluororubber layer 3 middle 矽 rubber Adhesive layer 4 Reinforcement in 矽 rubber layer 5 Fluororubber layer 6 Middle 矽 rubber layer 7 Flange 1 0 1st extruder 1 0 a Upper 1st extruder 1 0 b 1st extruder -26- (23) 1259882 11 Knitting machine 12 2nd extruder 13 Organic decane coupling agent coating machine 14 Drying process 20 Preparation of fluororubber sheet 2 1 Intermediate 矽 rubber coating " 22 Reinforcement entanglement of the top sheet of enamel rubber.

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Claims (1)

1259882 (1) Pickup, Patent Application No. 1 · A rubber hose for a rubber hose which is laminated on the outer periphery of the inner rubber layer by means of an extrusion method, and is characterized in that the inner rubber layer is a fluororubber layer And the outer rubber layer is woven into the rubber layer of the reinforcing yarn in which the reinforcing yarn is woven, and the fluororubber layer and the reinforcing yarn are woven between the rubber layers, and the adhesive composition containing the fluororubber layer is disposed. The intermediate rubber layer is such that the intermediate rubber layer is an intermediate rubber layer having a lower hardness than the reinforcing yarn woven into the enamel rubber layer and the fluororubber layer. 2 · The rubber hose of claim 1 of the patent scope, wherein the fluororubber is composed of a terpolymer (vinylidene fluoride, hexafluoropropylene, and tetrafluoropropene) or a copolymer of tetrafluoroethylene and propylene. Composition. 3 · For the rubber hose of the scope of claim 1, the thickness of the fluororubber layer is set to 0. 2~1 · 5 mm. 4. The rubber hose of claim 1 wherein the intermediate rubber layer is a rubber having a lower hardness than the reinforced rubber layer and the innermost layer of the fluororubber layer, and the hardness of the material is J IS A hardness of 10 to 30. . 5. The rubber hose of claim 1, wherein the thickness of the intermediate rubber layer is set to 0. 3 to 2 mm. 6. The rubber hose of claim 1, wherein 5 to 40 parts by weight of the aromatic polyamide short fibers are blended on the fluororubber layer based on 100 parts of the base polymer. 7. The rubber hose of claim 1, wherein the 矽 5 to 1 part by weight of the eucalyptus oil is blended on the fluororubber layer based on 100 parts of the base polymer. -28 - (2) 1259882 8. The rubber hose of claim 1 of the patent scope, wherein 2 to 15 parts by weight of magnesium oxide is blended in the middle 5 eve rubber based on 1 ο 原料 of the base polymer On the floor. 9 · The rubber hose of claim 1 of the patent scope, wherein 1 to 15 parts by weight of triallyl cyanurate is blended in the middle ruthenium rubber layer on the basis of 1 〇 0 parts of the base polymer on. 1 〇·If the rubber hose of the first application of the patent scope is Φ, based on 100 parts of the base polymer, the 矽·5~1 〇 part by weight of the organic decane coupling agent is blended on the middle ruthenium rubber layer. . 1 1 . The rubber hose of claim 1, wherein the rubber rubber layer is externally inserted on the inner circumference of the opposite pipe portion, and the crepe release agent 〇 1 2 is applied. The rubber hose of the item, wherein the fluororubber layer is externally inserted on the inner circumference of the opposite tube portion, and a plurality of flanges are protruded in the circumferential direction. A rubber hose according to claim 1, wherein an organic decane-based adhesive is applied between the gas rubber layer and the intermediate rubber layer. 1 4 · A method for manufacturing a rubber hose, wherein a fluororubber layer and a reinforcing yarn of the outer periphery thereof are woven between the ruthenium rubber layers, and a fluororubber layer which is woven into the ruthenium rubber layer and the innermost layer is disposed lower than the reinforcing yam A method for producing a rubber hose in which a middle rubber layer of a hardness is extruded in a state in which a fluororubber layer is extruded by a first extruder and a component corresponding to the fluororubber layer is contained in a laminated state, and the ratio is The fluororubber layer and the outer peripheral reinforcing yarn are woven into the middle of the lower hardness of the enamel rubber layer, and the reinforcing yarn is woven into the lower layer of -29-(3) 1259882 矽 rubber, and then supplied to the knitting machine, by the knitting machine, The reinforcing yarn is woven into the outer periphery of the lower layer of the reinforced rubber, and then supplied to the second extruder, and the reinforcing yarn is woven into the upper layer of the reinforced rubber and covered on the outer periphery of the woven reinforcing yarn by the second extruder. . 1 5 The method for producing a rubber hose according to claim 14 wherein the reinforcing yarn is woven and the side or both sides of the upper layer of the rubber are multi-layered. 1 6 The method for manufacturing a rubber hose according to claim 14 is to apply an organic decane coupling agent to the periphery of the fluororubber layer, wherein the fluororubber layer and ratio of the first extruder are used. The fluororubber layer and the reinforcing yam are woven into the ruthenium rubber layer and the intermediate ruthenium rubber layer and the reinforced woven fabric are woven into the lower layer of the ruthenium rubber layer, and are extruded by the fluororubber layer of the first first extruder, and are organically The application of the organic decane coupling agent of the decane coupling agent coater is carried out by extruding the intermediate ruthenium rubber layer of the first extruder and the reinforcing yarn into the lower layer of the ruthenium rubber. The rubber hose is a rubber hose which is formed by laminating an outer rubber layer on the outer circumference of the inner rubber layer by a winding method, and is characterized in that the inner rubber layer is a fluororubber layer and the outer rubber layer is provided. The layer is reinforced and arranged in the rubber layer, and between the fluororubber layer and the reinforcing rubber layer, an intermediate rubber layer containing the adhesive component with the fluororubber layer is disposed, and the intermediate rubber layer is reinforced. The middle ruthenium rubber layer of the lower hardness of the fluororubber which is placed in the ruthenium rubber layer and the innermost layer is disposed. 1 8 . The rubber hose of claim 17 wherein the fluororubber is composed of a terpolymer (vinylidene fluoride, and hexafluoropropylene, and tetrafluoropropan-30-(4) 1259882 ene), or It is composed of a copolymer of tetrafluoroethylene and propylene. 1 9 · The rubber hose of the Clause 7 of the patent application' has a thickness of 0. 2 to 1.5 mm. 2 0 · The rubber hose of Article 17 of the patent application' wherein the middle 矽 rubber layer is a rubber having a lower hardness than the reinforced rubber layer and the fluororubber layer, and the hardness of the material is 10 IS 30. 2 1 · For the rubber hose of claim 17 of the patent application, the thickness of the intermediate rubber layer is set to 0.3 mm to 2 mm. 2 2. A rubber hose according to claim 17 of the patent application, wherein 5 to 40 parts by weight of aromatic polyamine short fibers are blended on the fluororubber layer based on 100 parts of the base polymer. . 2 3. A rubber hose according to claim 17 of the patent application, wherein 0.5 to 10 parts by weight of eucalyptus oil is blended on the fluororubber layer based on 100 parts of the base polymer. 2 4 . The rubber hose of claim 17 of the patent application, wherein 2 to 15 parts by weight of magnesium oxide is blended on the intermediate rubber layer based on 100 parts of the base polymer. 2 5 · The rubber hose of claim 17 of the patent application, wherein 1 to 15 parts by weight of triallyl cyanurate is blended in the middle based on 100 parts of the base polymer. On the rubber layer. 2 6 . The rubber hose of claim 17 of the patent application, wherein 5 to 10 parts by weight of the organic decane coupling agent is blended on the intermediate rubber layer based on 100 parts of the base polymer. 2 7 · For the rubber hose of Clause No. 17 of the patent application, in which the fluororubber layer is externally inserted on the inner circumference of the opposite pipe portion, a bismuth release agent is applied. 2 8 . The rubber hose of claim 17, wherein the fluororubber layer is externally inserted into the inner circumference of the opposite tube portion, and a plurality of flanges are protruded in the circumferential direction. 2 9 . The rubber hose of claim 17 of the patent application, wherein an organic decane-based adhesive is applied between the fluororubber layer and the intermediate ruthenium rubber layer. 3 〇 · For the rubber hose of Clause No. 17 of the patent application, the outer peripheral surface of the fluororubber layer is embossed. 3 1 · A method for manufacturing a rubber hose is provided for the fluororubber layer and its outer periphery to be placed between the ruthenium rubber layers, and is configured to have a lower hardness than the reinforced rubber layer and the fluororubber layer. A method for producing a rubber hose comprising a winding method of arranging the above-mentioned fluororubber and reinforcing the intermediate enamel rubber layer of the ruthenium rubber and the subsequent component, wherein the fluororubber layer is formed by a calender roll and incorporated into the middle After laminating the rubber, a laminated sheet of a fluororubber layer sheet and an intermediate ruthenium rubber layer sheet is formed, and on the laminated sheet, a pre-formed top sheet reinforced with rubber is wound. 3 . The method for manufacturing a rubber hose according to claim 31, wherein the organic decane-based adhesive is applied to the outer periphery of the fluororubber layer, wherein the organic decane is coated after the fluororubber layer is formed. The adhesive is then mixed with the intermediate rubber to form a laminated sheet of the fluororubber layer sheet and the intermediate ruthenium rubber sheet. -32-