WO2014156666A1 - High-pressure hydraulic hose - Google Patents

High-pressure hydraulic hose Download PDF

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Publication number
WO2014156666A1
WO2014156666A1 PCT/JP2014/056599 JP2014056599W WO2014156666A1 WO 2014156666 A1 WO2014156666 A1 WO 2014156666A1 JP 2014056599 W JP2014056599 W JP 2014056599W WO 2014156666 A1 WO2014156666 A1 WO 2014156666A1
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WO
WIPO (PCT)
Prior art keywords
rubber
layer
rubber layer
hydraulic hose
reinforcing
Prior art date
Application number
PCT/JP2014/056599
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French (fr)
Japanese (ja)
Inventor
神戸　忍
暖志 永原
広志 西田
Original Assignee
東海ゴム工業株式会社
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Publication of WO2014156666A1 publication Critical patent/WO2014156666A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/081—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles

Definitions

  • the present invention relates to a high-pressure hydraulic hose, and more particularly to a high-pressure hydraulic hose for construction machinery (construction machinery) and mining machinery.
  • high-pressure hydraulic hoses for construction machinery and mining machinery have a multi-layer structure in which a plurality of intermediate rubber layers and wire reinforcing layers are laminated alternately between the inner rubber layer and outer rubber layer to withstand high pressure. Is adopted. In order to improve the durability of the high-pressure hydraulic hose, it is necessary to firmly bond the wire reinforcing layer and a rubber layer (particularly an intermediate rubber layer) in contact with the wire reinforcing layer.
  • a hose that can be used for a high-pressure hydraulic hose for example, in a hose having a brass-plated wire or organic fiber as a reinforcing layer, at least an adhesive layer in contact with the reinforcing layer is 100 parts by weight of sulfur vulcanizable raw rubber
  • a hose comprising a rubber composition containing silica, a resorcin donor and a methylene donor, and further containing 0.1 to 15 parts by weight of an organic sulfur-containing compound (Patent Document 1). ).
  • a hose usable for the high pressure hydraulic hose for example, an acrylonitrile-butadiene having a nitrile content of 42% by mass or less and a nitrile content of 10 to 20% by mass in a total rubber component of 100% by mass.
  • SP value solubility parameter
  • a hose having a rubber layer made of a rubber composition for a hose containing 0.1 to 1 part by mass of cobalt as a cobalt amount and containing a specific sulfenamide vulcanization accelerator has also been proposed (patent) Reference 2).
  • the hoses described in Patent Document 1 and Patent Document 2 do not have sufficient adhesion between the wire reinforcing layer and the rubber layer, and do not use an adhesive (adhesive-less). Until now, there has been no technique for sufficiently bonding the two. Further, if the adhesion between the wire reinforcing layer and the rubber layer is inferior, the wire is not fixed by the rubber layer, and the wire moves or loosens, so that the durability is also inferior.
  • the present invention has been made in view of such circumstances, and does not use an adhesive (adhesive-less), has excellent adhesiveness between a reinforcing layer made of a plated wire and a rubber layer, and has improved durability.
  • an adhesive adhesive-less
  • the inventors of the present invention have made extensive studies in order to obtain a high-pressure hydraulic hose having excellent adhesion between a reinforcing layer made of plated wire and a rubber layer and improved durability.
  • NBR acrylonitrile butadiene rubber
  • C vulcanizing agent having a morpholine structure
  • the synergistic effect causes the adhesion between the wire reinforcing layer and the rubber layer, compared with the case where (B) or (C) is used alone. I found that the power improved dramatically.
  • the phenolic resin (B) modified with a functional group having a double bond has a function of chemically bonding to the plating wire of the reinforcing layer and also has a function of chemically bonding to the diene rubber (A).
  • the vulcanizing agent having a morpholine structure and the vulcanization accelerator having a morpholine structure (C) also has a function of chemically bonding to the plating wire of the reinforcing layer, and is also chemically bonded to the diene rubber (A). It has a function.
  • (B) has the property of firmly bonding to the plating wire of the reinforcing layer
  • (C) has the property of firmly bonding to the diene rubber (A)
  • (C) is chemically coupled with (B). The reason is considered to form a bond.
  • the double bond of the functional group of the phenolic resin (B) modified with the functional group having a double bond is chemically bonded to the double bond of the diene rubber (A). It is presumed that the phenolic hydroxyl group (B) is chemically bonded to the hydroxyl group of the plating wire of the reinforcing layer.
  • the oxygen atom having the morpholine structure in (C) is chemically bonded to the hydroxyl group of the plating wire of the reinforcing layer, and as (C), 2- (4'-morpholinodithio) benzothiazole) or 4,4'- When dithiodimorpholine is used, the S atom is presumed to be chemically bonded to the double bond of the diene rubber (A).
  • the high-pressure hydraulic hose of the present invention is a high-pressure hydraulic hose having an inner rubber layer through which a fluid passes, a reinforcing layer made of a plated wire positioned outside the rubber layer, and a rubber layer in contact with the reinforcing layer.
  • the layer is composed of a rubber composition containing the following (A) to (C).
  • the high-pressure hydraulic hose of the present invention has a configuration in which the rubber layer in contact with the reinforcing layer made of the plated wire is made of the rubber composition containing the above (A) to (C).
  • the phenolic resin (B) modified with a functional group having a double bond has a function of chemically bonding to the plating wire of the reinforcing layer, and also has a function of chemically bonding to the diene rubber (A).
  • At least one of the vulcanizing agent having a morpholine structure and the vulcanization accelerator having a morpholine structure (C) also has a function of chemically bonding to the plating wire of the reinforcing layer, and is also chemically bonded to the diene rubber (A). It has a function.
  • (B) has a property of firmly bonding to the plating wire of the reinforcing layer
  • (C) has a property of firmly bonding to the diene rubber (A)
  • (C) is chemically coupled to (B). Form a bond.
  • the high-pressure hydraulic hose of the present invention has excellent durability and excellent durability between the reinforcing layer made of plated wire and the rubber layer without using an adhesive.
  • (B) is a cashew-modified phenolic resin
  • adhesion between the reinforcing layer made of the plated wire and the rubber layer and the durability of the hose are further improved.
  • a reinforcing thread layer, an intermediate rubber layer, a reinforcing layer made of plated wire, and an outer rubber layer are sequentially formed on the outer peripheral surface of the inner rubber layer, and the intermediate rubber layer contains the above (A) to (C)
  • the high-pressure hydraulic hose made of the rubber composition is excellent in adhesion between the reinforcing layer made of the plated wire and the intermediate rubber layer.
  • hydraulic hose of the present invention As the high-pressure hydraulic hose of the present invention (hereinafter sometimes simply referred to as “hydraulic hose”), for example, as shown in FIG. 1, a reinforcing yarn layer 2 is formed on the outer peripheral surface of the inner rubber layer 1, An intermediate rubber layer 3 is formed on the outer peripheral surface, a reinforcing layer 4 made of a plating wire is formed on the outer peripheral surface, and an outer rubber layer 5 is formed on the outer peripheral surface.
  • mineral oil such as hydraulic oil is used as hydraulic oil.
  • the high-pressure hydraulic hose of the present invention has a laminated structure in which the intermediate rubber layer 3 and the reinforcing layer 4 are alternately and repeatedly laminated.
  • the laminated structure of the intermediate rubber layer 3 and the reinforcing layer 4 has the above structure. Not limited to one layer (intermediate rubber layer 3 / reinforcing layer 4) shown in FIG.
  • the rubber layer (preferably the intermediate rubber layer 3) in contact with the reinforcing layer 4 made of the plated wire is made of a rubber composition containing the following (A) to (C). It is.
  • diene rubber (A) examples include natural rubber (NR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), isoprene rubber (IR), butadiene rubber (BR), and the like. These may be used alone or in combination of two or more. Of these, NBR is preferable when oil resistance is required, and SBR and NR are preferable when wear resistance is required. In addition, NBR is preferable that the acrylonitrile content (bonded AN amount) does not exceed 33% from the viewpoint of adhesiveness.
  • Phenolic resin modified with a functional group having a double bond examples include cashew-modified phenolic resins such as cashew-modified phenol novolac resin, oil-modified phenolic resins, and the like. These may be used alone or in combination of two or more. Among these, cashew-modified phenol resin is preferable from the viewpoint of compatibility with the diene rubber (A), and cashew oil-modified / phenol / formaldehyde polycondensate is particularly preferable.
  • a specific example of the cashew oil-modified phenol-formaldehyde polycondensate is Sumitrite Resin PR-12686 manufactured by Sumitomo Bakelite.
  • the content of the specific phenolic resin (B) is preferably in the range of 2 to 15 parts by weight, particularly preferably 2 to 8 parts by weight with respect to 100 parts by weight of the diene rubber (A). If the content of the specific phenolic resin (B) is too small, the adhesiveness between the intermediate rubber layer and the reinforcing layer made of the plated wire tends to be deteriorated. There is a tendency that aging resistance and sag resistance deteriorate.
  • Vulcanizing agent having morpholine structure (C) >> Examples of the vulcanizing agent (C) having the morpholine structure include 4,4′-dithiodimorpholine and the like, and specifically, Barnock R manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
  • Vulcanization accelerator having morpholine structure (C) Examples of the vulcanization accelerator (C) having the morpholine structure include 2- (4′-morpholinodithio) benzothiazole, N-oxydiethylene-2-benzothiazolylsulfenamide, and the like. These may be used alone or in combination of two or more. Among these, 2- (4′-morpholinodithio) benzothiazole is preferable from the viewpoint of reactivity with the diene rubber (A), and specifically, Noxeller MDB manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. It is done.
  • the content of (C) is preferably in the range of 0.2 to 4 parts by weight, particularly preferably 1 to 3 parts by weight with respect to 100 parts by weight of the diene rubber (A). If the content of (C) is too small, the adhesion between the intermediate rubber layer and the reinforcing layer made of the plated wire tends to deteriorate, and if it is too large, the physical properties, heat aging resistance, and set resistance are poor. There is a tendency to become.
  • the rubber composition for forming the intermediate rubber layer includes zinc oxide, stearic acid, carbon black, silica, plasticizer, process oil, processing aid, and (C )
  • vulcanization accelerators other than the above (C), etc. may be appropriately blended as necessary.
  • higher adhesiveness can be obtained by adding silica (particularly acidic silica).
  • the rubber composition for forming the intermediate rubber layer is prepared by appropriately adding additives such as zinc oxide in addition to (A) to (C) as necessary, and kneaders, rolls, Banbury mixers, etc. It can be prepared by kneading using a kneader.
  • the reinforcing layer 4 is a layer formed by braiding a plating wire into a blade shape, a spiral shape or the like in order to reinforce the strength of the entire hose.
  • the reinforcing layer 4 is not limited to one layer as described above, and may be two or more layers.
  • Examples of the plating treatment for the plating wire include copper plating, zinc plating, brass (copper-zinc alloy) plating, nickel plating, tin plating, and cobalt plating, and brass plating is preferable.
  • the diameter of the plating wire is usually in the range of 0.15 to 1.00 mm, preferably in the range of 0.20 to 0.80 mm.
  • the rubber forming the inner rubber layer 1 is preferably a rubber excellent in oil resistance.
  • the rubber composition for forming the inner rubber layer includes a reinforcing material (carbon black and the like), a white filler, a plasticizer, stearic acid, zinc white, a vulcanizing agent, and vulcanization acceleration. Agents, processing aids, etc. may be appropriately blended as necessary.
  • the rubber forming the outer rubber layer 5 is preferably a rubber having excellent weather resistance, such as chloroprene rubber (CR), styrene butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), SBR and EPDM.
  • CR is preferable from the viewpoint of weather resistance, cost, and oil resistance.
  • the rubber composition for forming the outer surface rubber layer includes a reinforcing material (carbon black, etc.), white filler, plasticizer, stearic acid, zinc white, acid acceptor (highly activated) Magnesium, hydrotalcite, etc.), anti-aging agents, vulcanizing agents, vulcanizing agent accelerators, processing aids and the like may be added as necessary.
  • a reinforcing material carbon black, etc.
  • white filler plasticizer
  • stearic acid zinc white
  • anti-aging agents vulcanizing agents, vulcanizing agent accelerators, processing aids and the like may be added as necessary.
  • the phenolic resin (B) modified with the functional group having the double bond is also applied to the rubber composition for forming the outer rubber layer.
  • at least one of a vulcanizing agent having a morpholine structure and a vulcanization accelerator having a morpholine structure (C) may be used in combination. In this case, adhesion between the reinforcing layer 4 made of plated wire and the outer rubber layer 5 And the interlayer adhesion of the entire hose is improved.
  • reinforcing thread layer examples of the reinforcing yarn forming the reinforcing yarn layer 2 include vinylon (polyvinyl alcohol) yarn, polyamide (nylon) yarn, aramid yarn, polyethylene terephthalate (PET) yarn and the like. Among these, polyamide yarn is preferable from the viewpoint of high strength and high modulus.
  • Examples of the method for braiding the reinforcing yarn include spiral knitting and blade knitting.
  • the hydraulic hose of the present invention can be manufactured, for example, as follows. That is, first, the rubber composition for forming the inner rubber layer is extruded onto a mandrel using an extruder to mold the inner rubber layer 1. Next, a reinforcing yarn layer 2 is formed on the outer peripheral surface of the inner rubber layer 1 by winding a reinforcing yarn such as polyamide yarn in a blade shape using a braiding machine. Subsequently, the intermediate rubber layer 3 is formed by extruding the rubber composition for forming the intermediate rubber layer onto the outer peripheral surface of the reinforcing yarn layer 2. Next, the reinforcing layer 4 is formed on the outer peripheral surface of the intermediate rubber layer 3 by braiding brass plating wires in a spiral shape.
  • the outer rubber layer 5 is formed by extruding the rubber composition for forming the outer rubber layer on the outer peripheral surface of the reinforcing layer 4. Further, a polyamide canvas is wound around the outer peripheral surface of the outer rubber layer 5 in a spiral shape. Finally, the laminate is vulcanized (steam vulcanized, etc.) under predetermined conditions (eg, 140 to 170 ° C. ⁇ 10 to 60 minutes), and the polyamide canvas is removed, as shown in FIG. Such a five-layer hydraulic hose can be produced.
  • the hydraulic hose of the present invention is not limited to the five-layer structure as shown in FIG. 1, but has a structure in which two or more intermediate rubber layers 3 and reinforcing layers 4 are alternately laminated as described above. There is no problem.
  • the hose inner diameter is usually in the range of 5 to 85 mm, preferably in the range of 6 to 80 mm, and the hose outer diameter is usually in the range of 9 to 100 mm, preferably in the range of 10 to 85 mm. is there.
  • the inner rubber layer 1 has a thickness of usually 0.7 to 4.0 mm, preferably 1.0 to 3.0 mm, and the intermediate rubber layer 3 has a thickness of 0.1 to 0.5 mm.
  • the thickness is preferably in the range of 0.2 to 0.4 mm, and the thickness of the outer rubber layer 5 is usually in the range of 0.5 to 2.5 mm, preferably in the range of 0.8 to 2.0 mm. It is.
  • Nipol DN401 bound nitrile content: 18%), manufactured by Nippon Zeon [SBR] JBR, SBR1500 [NR] RSS # 3 (w28350)
  • Nipol DN302 bound nitrile content: 28%), manufactured by Nippon Zeon [NBR] Nipol DN3350 (amount of bound nitrile: 33%) manufactured by ZEON Corporation
  • Phenolic resin modified with a functional group having a double bond (B) >> [Cashew oil modified phenol / formaldehyde polycondensate] Sumilite resin PR-12686, manufactured by Sumitomo Bakelite Co., Ltd.
  • Example 1 to 10 Comparative Examples 1 to 5
  • Table 1 and Table 2 The components shown in Table 1 and Table 2 below were blended in the proportions shown in the table, and these were kneaded using a 3 L kneader to prepare a rubber composition.
  • the rubber 11 of this vulcanized adhesion sample and the brass plating wire 12 are chucked, and the brass plating wire 12 is peeled off in the X direction in accordance with the JIS K6256 T-type peeling test, and the rubber on the surface of the brass plating wire 12 A coverage of 11 was measured. It shows that the adhesiveness of rubber
  • Examples 1 to 10 have higher rubber coverage on the brass plated wire surface and better adhesion between rubber and brass plated wire than Comparative Examples 1 to 5. I found out.
  • Example 11 An 11-layer hydraulic hose (inner diameter: 19 mm) made of the material shown in Table 3 below was produced.
  • each layer was prepared as follows.
  • NBR manufactured by Nippon Zeon, Nipol DN202, amount of bonded AN: 31%), 5 parts by weight of zinc oxide (Mitsui Metal Mining Co., Ltd., 2 types of zinc oxide), stearic acid (manufactured by Kao Corporation, Lunac S30) 1 part by weight, anti-aging agent (Seiko Chemical Co., Ltd., Ozonon 3C) 2 parts by weight, anti-aging agent (Seiko Chemical Co., Ltd., non-flex BA) 2 parts by weight, FEF grade carbon black (Tokai Carbon Co., Ltd., Seast SO) ) 90 parts by weight, 15 parts by weight of a plasticizer (manufactured by ADEKA, Adekasizer RS-107), 2 parts by weight of a vulcanizing agent (manufactured by Karuizawa Seirakusho Co., Ltd., sulfur), tetramethylthiuram disulfide (
  • the NBR rubber composition for forming the inner rubber layer was extruded onto a mandrel to form an inner rubber layer.
  • a reinforcing yarn layer (polyamide yarn) was wound around the outer peripheral surface of the inner rubber layer using a braiding machine to form a reinforcing yarn layer.
  • the intermediate rubber layer (1) was formed by extruding the rubber composition 6 (see Table 1) for the intermediate rubber forming layer prepared in Example 6 on the outer peripheral surface of the reinforcing yarn layer.
  • a brass-plated wire (diameter 0.4 mm) was braided in a spiral shape to form a reinforcing layer (1).
  • This operation was repeated to form an intermediate rubber layer (2) / reinforcing layer (2) / intermediate rubber layer (3) / reinforcing layer (3) / intermediate rubber layer (4) / reinforcing layer (4).
  • the outer rubber layer was formed by extruding the CR rubber composition for forming the outer rubber layer on the outer peripheral surface of the reinforcing layer (4).
  • a polyamide canvas was wound around the outer peripheral surface of the outer rubber layer in a spiral shape.
  • the laminate was steam vulcanized at 150 ° C. for 60 minutes, and then the polyamide canvas was removed to produce an 11-layer hydraulic hose (inner diameter: 19 mm) shown in Table 3 above.
  • Toxen Co., Ltd. was used as a brass plating wire.
  • Example 12 As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Example 7 (see Table 1) in place of the rubber composition of Example 6, and this was carried out. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
  • Example 13 As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Example 10 (see Table 1) in place of the rubber composition of Example 6, and this was carried out. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
  • the high-pressure hydraulic hose of the present invention can be used for all hoses that require pressure resistance.
  • it can be used for construction equipment, mining machinery, industrial vehicles (forklifts, automatic guided vehicles, etc.), It is suitably used as a high-pressure hydraulic hose for mining machines.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a high-pressure hydraulic hose which has improved durability, exhibits excellent adhesion between a rubber layer and a reinforcing layer comprising a plated wire, and does not use an adhesive (adhesive-less). The high-pressure hydraulic hose has an inner-surface rubber layer (1), a reinforcing layer (4) comprising a plated wire and positioned on the outside thereof, and a rubber layer (3) which contacts the reinforcing layer (4). Therein, the rubber layer (3) comprises a rubber composition containing components ((A)-(C)). (A) A diene rubber. (B) A phenolic resin modified with a functional group having a double bond. (C) A vulcanizing agent having a morpholine structure, and/or a vulcanization accelerator having a morpholine structure.

Description

高圧油圧ホースHigh pressure hydraulic hose
　本発明は、高圧油圧ホースに関するものであり、詳しくは、建設機械（建機）、鉱山（マイニング）機械向けの高圧油圧ホースに関するものである。 The present invention relates to a high-pressure hydraulic hose, and more particularly to a high-pressure hydraulic hose for construction machinery (construction machinery) and mining machinery.
　一般に、建機、マイニング機械向けの高圧油圧ホースは、高い圧力に耐えるため、内面ゴム層と外面ゴム層との間に、中間ゴム層とワイヤー補強層とを交互に複数積層してなる多層構造が採用されている。高圧油圧ホースの耐久性を向上させるためには、ワイヤー補強層と、これに接するゴム層（特に、中間ゴム層）とを強固に接着する必要がある。 Generally, high-pressure hydraulic hoses for construction machinery and mining machinery have a multi-layer structure in which a plurality of intermediate rubber layers and wire reinforcing layers are laminated alternately between the inner rubber layer and outer rubber layer to withstand high pressure. Is adopted. In order to improve the durability of the high-pressure hydraulic hose, it is necessary to firmly bond the wire reinforcing layer and a rubber layer (particularly an intermediate rubber layer) in contact with the wire reinforcing layer.
　従来、高圧油圧ホースに使用可能なホースとしては、例えば、黄銅メッキワイヤーまたは有機繊維を補強層として有するホースにおいて、少なくとも前記補強層に接する接着層を、イオウ加硫可能な原料ゴム１００重量部に対し、シリカ、レゾルシン供与体およびメチレン供与体を配合し、さらに有機含硫黄化合物を０．１～１５重量部配合してなるゴム組成物で構成してなるホースが提案されている（特許文献１）。また、上記高圧油圧ホースに使用可能なホースとしては、例えば、ニトリル含量が４２質量％以下であって、ゴム成分全量１００質量％中にニトリル含量が１０～２０質量％となる量のアクリロニトリル－ブタジエンゴム（ＮＢＲ）と、溶解パラメーター（ＳＰ値）が１５～１９(ＭＰａ)1/2である１０～４０質量％の量の非極性ゴムとを含有するゴム成分１００質量部に対し、コバルト含有化合物をコバルト量として０．１～１質量部の量で含有し、かつ特定のスルフェンアミド系加硫促進剤を含有するホース用ゴム組成物からなるゴム層を有するホースも提案されている（特許文献２）。 Conventionally, as a hose that can be used for a high-pressure hydraulic hose, for example, in a hose having a brass-plated wire or organic fiber as a reinforcing layer, at least an adhesive layer in contact with the reinforcing layer is 100 parts by weight of sulfur vulcanizable raw rubber On the other hand, there has been proposed a hose comprising a rubber composition containing silica, a resorcin donor and a methylene donor, and further containing 0.1 to 15 parts by weight of an organic sulfur-containing compound (Patent Document 1). ). As a hose usable for the high pressure hydraulic hose, for example, an acrylonitrile-butadiene having a nitrile content of 42% by mass or less and a nitrile content of 10 to 20% by mass in a total rubber component of 100% by mass. Cobalt-containing compound for 100 parts by mass of rubber component containing rubber (NBR) and nonpolar rubber in an amount of 10-40% by mass with a solubility parameter (SP value) of 15-19 (MPa) 1/2 A hose having a rubber layer made of a rubber composition for a hose containing 0.1 to 1 part by mass of cobalt as a cobalt amount and containing a specific sulfenamide vulcanization accelerator has also been proposed (patent) Reference 2).
特公平６－８４７９３号公報Japanese Patent Publication No. 6-84793 特開２０１１－１５２４号公報JP 2011-1524 A
　しかしながら、上記特許文献１および特許文献２に記載のホースは、ワイヤー補強層とゴム層との接着性が充分ではなく、接着剤を使用しない（接着剤レス）で、ワイヤー補強層とゴム層とを充分に接着させる技術はこれまで存在しなかった。また、ワイヤー補強層とゴム層との接着性が劣ると、ワイヤーがゴム層で固定されておらず、ワイヤーが動いたり、緩んだりするため、耐久性の点でも劣っていた。 However, the hoses described in Patent Document 1 and Patent Document 2 do not have sufficient adhesion between the wire reinforcing layer and the rubber layer, and do not use an adhesive (adhesive-less). Until now, there has been no technique for sufficiently bonding the two. Further, if the adhesion between the wire reinforcing layer and the rubber layer is inferior, the wire is not fixed by the rubber layer, and the wire moves or loosens, so that the durability is also inferior.
　本発明は、このような事情に鑑みなされたもので、接着剤を使用しない（接着剤レス）で、メッキワイヤーからなる補強層とゴム層との接着性に優れ、耐久性が向上した高圧油圧ホースを提供する。 The present invention has been made in view of such circumstances, and does not use an adhesive (adhesive-less), has excellent adhesiveness between a reinforcing layer made of a plated wire and a rubber layer, and has improved durability. Provide a hose.
　本発明者らは、メッキワイヤーからなる補強層とゴム層との接着性に優れ、耐久性が向上した高圧油圧ホースを得るため、鋭意研究を重ねた。その研究の過程で、アクリロニトリルブタジエンゴム（ＮＢＲ）等のジエン系ゴム（Ａ）に、二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）と、モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方（Ｃ）とを併用すると、その相乗効果により、（Ｂ）もしくは（Ｃ）をそれぞれ単独で使用する場合に比べて、ワイヤー補強層とゴム層との接着力が飛躍的に向上することを見いだした。 The inventors of the present invention have made extensive studies in order to obtain a high-pressure hydraulic hose having excellent adhesion between a reinforcing layer made of plated wire and a rubber layer and improved durability. In the course of the research, a phenolic resin (B) modified with a functional group having a double bond to a diene rubber (A) such as acrylonitrile butadiene rubber (NBR), a vulcanizing agent having a morpholine structure, and morpholine When used in combination with at least one of the vulcanization accelerators having a structure (C), the synergistic effect causes the adhesion between the wire reinforcing layer and the rubber layer, compared with the case where (B) or (C) is used alone. I found that the power improved dramatically.
　この機序は明らかではないが、以下のように推測される。すなわち、二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）は、補強層のメッキワイヤーと化学結合する機能を有するとともに、ジエン系ゴム（Ａ）とも化学結合する機能を有する。また、モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方（Ｃ）も、補強層のメッキワイヤーと化学結合する機能を有するとともに、ジエン系ゴム（Ａ）とも化学結合する機能を有する。特に、（Ｂ）は補強層のメッキワイヤーと強固に結合する性質があり、（Ｃ）はジエン系ゴム（Ａ）と強固に結合する性質があり、かつ、（Ｃ）が（Ｂ）とも化学結合を形成することがその理由と考えられる。 This mechanism is not clear, but is presumed as follows. That is, the phenolic resin (B) modified with a functional group having a double bond has a function of chemically bonding to the plating wire of the reinforcing layer and also has a function of chemically bonding to the diene rubber (A). Further, at least one of the vulcanizing agent having a morpholine structure and the vulcanization accelerator having a morpholine structure (C) also has a function of chemically bonding to the plating wire of the reinforcing layer, and is also chemically bonded to the diene rubber (A). It has a function. In particular, (B) has the property of firmly bonding to the plating wire of the reinforcing layer, (C) has the property of firmly bonding to the diene rubber (A), and (C) is chemically coupled with (B). The reason is considered to form a bond.
　より具体的には、二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）の官能基の二重結合が、ジエン系ゴム（Ａ）の二重結合と化学的に結合するとともに、（Ｂ）のフェノール性水酸基が、補強層のメッキワイヤーの水酸基と化学的に結合すると推測される。また、（Ｃ）のモルホリン構造の酸素原子が、補強層のメッキワイヤーの水酸基と化学的に結合するとともに（Ｃ）として、２－（４′－モルホリノジチオ）ベンゾチアゾール）や４，４′－ジチオジモルホリンを使用した場合には、そのＳ原子が、ジエン系ゴム（Ａ）の二重結合と化学的に結合すると推測される。 More specifically, the double bond of the functional group of the phenolic resin (B) modified with the functional group having a double bond is chemically bonded to the double bond of the diene rubber (A). It is presumed that the phenolic hydroxyl group (B) is chemically bonded to the hydroxyl group of the plating wire of the reinforcing layer. In addition, the oxygen atom having the morpholine structure in (C) is chemically bonded to the hydroxyl group of the plating wire of the reinforcing layer, and as (C), 2- (4'-morpholinodithio) benzothiazole) or 4,4'- When dithiodimorpholine is used, the S atom is presumed to be chemically bonded to the double bond of the diene rubber (A).
　すなわち、本発明の高圧油圧ホースは、流体を通す内面ゴム層と、その外側に位置するメッキワイヤーからなる補強層と、この補強層に接するゴム層とを有する高圧油圧ホースであって、上記ゴム層が、下記の（Ａ）～（Ｃ）を含有するゴム組成物からなるという構成をとる。
（Ａ）ジエン系ゴム。
（Ｂ）二重結合を有する官能基で変性されたフェノール系樹脂。
（Ｃ）モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方。 That is, the high-pressure hydraulic hose of the present invention is a high-pressure hydraulic hose having an inner rubber layer through which a fluid passes, a reinforcing layer made of a plated wire positioned outside the rubber layer, and a rubber layer in contact with the reinforcing layer. The layer is composed of a rubber composition containing the following (A) to (C).
(A) Diene rubber.
(B) A phenolic resin modified with a functional group having a double bond.
(C) At least one of a vulcanizing agent having a morpholine structure and a vulcanization accelerator having a morpholine structure.
　以上のように、本発明の高圧油圧ホースは、メッキワイヤーからなる補強層に接するゴム層が、上記（Ａ）～（Ｃ）を含有するゴム組成物からなるという構成をとる。二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）は、補強層のメッキワイヤーと化学結合する機能を有するとともに、ジエン系ゴム（Ａ）とも化学結合する機能を有する。また、モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方（Ｃ）も、補強層のメッキワイヤーと化学結合する機能を有するとともに、ジエン系ゴム（Ａ）とも化学結合する機能を有する。特に、（Ｂ）は補強層のメッキワイヤーと強固に結合する性質があり、（Ｃ）はジエン系ゴム（Ａ）と強固に結合する性質があり、かつ、（Ｃ）は（Ｂ）とも化学結合を形成する。これらのことから、本発明の高圧油圧ホースは、接着剤を使用することなく、メッキワイヤーからなる補強層とゴム層との接着性に優れ、優れた耐久性を奏する。 As described above, the high-pressure hydraulic hose of the present invention has a configuration in which the rubber layer in contact with the reinforcing layer made of the plated wire is made of the rubber composition containing the above (A) to (C). The phenolic resin (B) modified with a functional group having a double bond has a function of chemically bonding to the plating wire of the reinforcing layer, and also has a function of chemically bonding to the diene rubber (A). Further, at least one of the vulcanizing agent having a morpholine structure and the vulcanization accelerator having a morpholine structure (C) also has a function of chemically bonding to the plating wire of the reinforcing layer, and is also chemically bonded to the diene rubber (A). It has a function. In particular, (B) has a property of firmly bonding to the plating wire of the reinforcing layer, (C) has a property of firmly bonding to the diene rubber (A), and (C) is chemically coupled to (B). Form a bond. For these reasons, the high-pressure hydraulic hose of the present invention has excellent durability and excellent durability between the reinforcing layer made of plated wire and the rubber layer without using an adhesive.
　また、上記（Ｂ）が、カシュー変性フェノール系樹脂であると、メッキワイヤーからなる補強層とゴム層との接着性、ホースの耐久性がさらに向上する。 Further, when (B) is a cashew-modified phenolic resin, the adhesion between the reinforcing layer made of the plated wire and the rubber layer and the durability of the hose are further improved.
　さらに、上記（Ｃ）が、モルホリン構造を有するチアゾール系加硫促進剤であると、メッキワイヤーからなる補強層とゴム層との接着性、ホースの耐久性がより一層向上する。 Furthermore, when the above (C) is a thiazole vulcanization accelerator having a morpholine structure, the adhesion between the reinforcing layer made of the plated wire and the rubber layer and the durability of the hose are further improved.
　そして、内面ゴム層の外周面に補強糸層、中間ゴム層、メッキワイヤーからなる補強層、外面ゴム層が順次形成されてなり、上記中間ゴム層が、上記（Ａ）～（Ｃ）を含有するゴム組成物からなる高圧油圧ホースは、メッキワイヤーからなる補強層と、中間ゴム層との接着性が優れている。 A reinforcing thread layer, an intermediate rubber layer, a reinforcing layer made of plated wire, and an outer rubber layer are sequentially formed on the outer peripheral surface of the inner rubber layer, and the intermediate rubber layer contains the above (A) to (C) The high-pressure hydraulic hose made of the rubber composition is excellent in adhesion between the reinforcing layer made of the plated wire and the intermediate rubber layer.
高圧油圧ホースの断面を示す模式図である。It is a schematic diagram which shows the cross section of a high pressure hydraulic hose. ゴムと黄銅メッキワイヤーとの接着性評価における、剥離試験を示す説明図である。It is explanatory drawing which shows the peeling test in the adhesiveness evaluation of rubber | gum and a brass plating wire.
　つぎに、本発明の実施の形態について詳しく説明する。ただし、本発明は、この実施の形態に限られるものではない。 Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.
　本発明の高圧油圧ホース（以下、単に「油圧ホース」と略する場合もある。）としては、例えば、図１に示すように、内面ゴム層１の外周面に補強糸層２が形成され、その外周面に中間ゴム層３が形成され、その外周面にメッキワイヤーからなる補強層４が形成され、さらにその外周面に外面ゴム層５が形成されたものがあげられる。油圧ホース内を流れる流体としては、例えば、作動油等の鉱物油が使用される。 As the high-pressure hydraulic hose of the present invention (hereinafter sometimes simply referred to as “hydraulic hose”), for example, as shown in FIG. 1, a reinforcing yarn layer 2 is formed on the outer peripheral surface of the inner rubber layer 1, An intermediate rubber layer 3 is formed on the outer peripheral surface, a reinforcing layer 4 made of a plating wire is formed on the outer peripheral surface, and an outer rubber layer 5 is formed on the outer peripheral surface. As the fluid flowing in the hydraulic hose, for example, mineral oil such as hydraulic oil is used.
　なお、本発明の高圧油圧ホースにおいては、上記中間ゴム層３と補強層４とが交互に繰り返し積層してなる積層構造を有するが、中間ゴム層３と補強層４との積層構造は、上記図１に示した１層（中間ゴム層３／補強層４）に限定されず、２層（中間ゴム層３／補強層４／中間ゴム層３／補強層４）、３層（中間ゴム層３／補強層４／中間ゴム層３／補強層４／中間ゴム層３／補強層４）、４層（中間ゴム層３／補強層４／中間ゴム層３／補強層４／中間ゴム層３／補強層４／中間ゴム層３／補強層４）、もしくは５層以上であっても差し支えない。 The high-pressure hydraulic hose of the present invention has a laminated structure in which the intermediate rubber layer 3 and the reinforcing layer 4 are alternately and repeatedly laminated. The laminated structure of the intermediate rubber layer 3 and the reinforcing layer 4 has the above structure. Not limited to one layer (intermediate rubber layer 3 / reinforcing layer 4) shown in FIG. 1, two layers (intermediate rubber layer 3 / reinforcing layer 4 / intermediate rubber layer 3 / reinforcing layer 4), three layers (intermediate rubber layer) 3 / reinforcing layer 4 / intermediate rubber layer 3 / reinforcing layer 4 / intermediate rubber layer 3 / reinforcing layer 4), 4 layers (intermediate rubber layer 3 / reinforcing layer 4 / intermediate rubber layer 3 / reinforcing layer 4 / intermediate rubber layer 3) / Reinforcing layer 4 / intermediate rubber layer 3 / reinforcing layer 4), or 5 layers or more.
　本発明においては、上記メッキワイヤーからなる補強層４に接するゴム層（好ましくは、中間ゴム層３）が、下記の（Ａ）～（Ｃ）を含有するゴム組成物からなることが最大の特徴である。
（Ａ）ジエン系ゴム。
（Ｂ）二重結合を有する官能基で変性されたフェノール系樹脂。
（Ｃ）モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方。 The greatest feature of the present invention is that the rubber layer (preferably the intermediate rubber layer 3) in contact with the reinforcing layer 4 made of the plated wire is made of a rubber composition containing the following (A) to (C). It is.
(A) Diene rubber.
(B) A phenolic resin modified with a functional group having a double bond.
(C) At least one of a vulcanizing agent having a morpholine structure and a vulcanization accelerator having a morpholine structure.
〔中間ゴム層〕
　まず、上記中間ゴム層形成用のゴム組成物の各成分について説明する。 [Intermediate rubber layer]
First, each component of the rubber composition for forming the intermediate rubber layer will be described.
《ジエン系ゴム（Ａ）》
　上記ジエン系ゴム（Ａ）としては、例えば、天然ゴム（ＮＲ）、スチレンブタジエンゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、耐油性が求められる場合は、ＮＢＲが好ましく、耐摩耗性が求められる場合は、ＳＢＲ、ＮＲが好ましい。なお、ＮＢＲは、接着性の点から、アクリロニトリル含有量（結合ＡＮ量）が３３％を超えないものが好ましい。 《Diene rubber (A)》
Examples of the diene rubber (A) include natural rubber (NR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), isoprene rubber (IR), butadiene rubber (BR), and the like. These may be used alone or in combination of two or more. Of these, NBR is preferable when oil resistance is required, and SBR and NR are preferable when wear resistance is required. In addition, NBR is preferable that the acrylonitrile content (bonded AN amount) does not exceed 33% from the viewpoint of adhesiveness.
《二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）》
　上記二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）としては、例えば、カシュー変性フェノールノボラック樹脂等のカシュー変性フェノール樹脂や、オイル変性フェノール樹脂等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、ジエン系ゴム（Ａ）との相溶性の点から、カシュー変性フェノール樹脂が好ましく、特に好ましくはカシューオイル変性・フェノール・ホルムアルデヒド重縮合物である。上記カシューオイル変性・フェノール・ホルムアルデヒド重縮合物の具体例としては、住友ベークライト社製のスミライトレジンＰＲ－１２６８６があげられる。 << Phenolic resin modified with a functional group having a double bond (B) >>
Examples of the phenolic resin (B) modified with the functional group having a double bond include cashew-modified phenolic resins such as cashew-modified phenol novolac resin, oil-modified phenolic resins, and the like. These may be used alone or in combination of two or more. Among these, cashew-modified phenol resin is preferable from the viewpoint of compatibility with the diene rubber (A), and cashew oil-modified / phenol / formaldehyde polycondensate is particularly preferable. A specific example of the cashew oil-modified phenol-formaldehyde polycondensate is Sumitrite Resin PR-12686 manufactured by Sumitomo Bakelite.
　上記特定のフェノール系樹脂（Ｂ）の含有量は、上記ジエン系ゴム（Ａ）１００重量部に対して、２～１５重量部の範囲が好ましく、特に好ましくは２～８重量部である。上記特定のフェノール系樹脂（Ｂ）の含有量が少なすぎると、中間ゴム層と、メッキワイヤーからなる補強層との接着性が悪くなる傾向がみられ、多すぎると、加工性、物性、耐熱老化性、耐ヘタリ性が悪くなる傾向がみられる。 The content of the specific phenolic resin (B) is preferably in the range of 2 to 15 parts by weight, particularly preferably 2 to 8 parts by weight with respect to 100 parts by weight of the diene rubber (A). If the content of the specific phenolic resin (B) is too small, the adhesiveness between the intermediate rubber layer and the reinforcing layer made of the plated wire tends to be deteriorated. There is a tendency that aging resistance and sag resistance deteriorate.
《モルホリン構造を有する加硫剤（Ｃ）》
　上記モルホリン構造を有する加硫剤（Ｃ）としては、例えば、４，４′－ジチオジモルホリン等があげられ、具体的には、大内新興化学工業社製のバルノックＲがあげられる。 << Vulcanizing agent having morpholine structure (C) >>
Examples of the vulcanizing agent (C) having the morpholine structure include 4,4′-dithiodimorpholine and the like, and specifically, Barnock R manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
《モルホリン構造を有する加硫促進剤（Ｃ）》
　上記モルホリン構造を有する加硫促進剤（Ｃ）としては、例えば、２－（４′－モルホリノジチオ）ベンゾチアゾール、Ｎ－オキシジエチレン－２－ベンゾチアゾリルスルフェンアミド等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、ジエン系ゴム(Ａ)との反応性の点から、２－（４′－モルホリノジチオ）ベンゾチアゾールが好ましく、具体的には、大内新興化学工業社製のノクセラーＭＤＢがあげられる。 << Vulcanization accelerator having morpholine structure (C) >>
Examples of the vulcanization accelerator (C) having the morpholine structure include 2- (4′-morpholinodithio) benzothiazole, N-oxydiethylene-2-benzothiazolylsulfenamide, and the like. These may be used alone or in combination of two or more. Among these, 2- (4′-morpholinodithio) benzothiazole is preferable from the viewpoint of reactivity with the diene rubber (A), and specifically, Noxeller MDB manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. It is done.
　上記（Ｃ）の含有量は、上記ジエン系ゴム（Ａ）１００重量部に対して、０．２～４重量部の範囲が好ましく、特に好ましくは１～３重量部である。上記（Ｃ）の含有量が少なすぎると、中間ゴム層と、メッキワイヤーからなる補強層との接着性が悪くなる傾向がみられ、多すぎると、物性、耐熱老化性、耐ヘタリ性が悪くなる傾向がみられる。 The content of (C) is preferably in the range of 0.2 to 4 parts by weight, particularly preferably 1 to 3 parts by weight with respect to 100 parts by weight of the diene rubber (A). If the content of (C) is too small, the adhesion between the intermediate rubber layer and the reinforcing layer made of the plated wire tends to deteriorate, and if it is too large, the physical properties, heat aging resistance, and set resistance are poor. There is a tendency to become.
　なお、上記中間ゴム層形成用のゴム組成物には、上記（Ａ）～（Ｃ）以外に、酸化亜鉛、ステアリン酸、カーボンブラック、シリカ、可塑剤、プロセスオイル、加工助剤、上記（Ｃ）以外の加硫剤（硫黄等）、上記（Ｃ）以外の加硫促進剤等を必要に応じて適宜に配合しても差し支えない。なお、シリカ（特に、酸性シリカ)の添加によって、より高い接着性が得られる。 In addition to the above (A) to (C), the rubber composition for forming the intermediate rubber layer includes zinc oxide, stearic acid, carbon black, silica, plasticizer, process oil, processing aid, and (C ) Other than (), vulcanization accelerators other than the above (C), etc. may be appropriately blended as necessary. In addition, higher adhesiveness can be obtained by adding silica (particularly acidic silica).
　上記中間ゴム層形成用のゴム組成物は、例えば、（Ａ）～（Ｃ）に加えて、酸化亜鉛等の添加剤を必要に応じて適宜に配合し、これらをニーダー，ロール，バンバリーミキサー等の混練機を用いて混練することにより、調製することができる。 The rubber composition for forming the intermediate rubber layer is prepared by appropriately adding additives such as zinc oxide in addition to (A) to (C) as necessary, and kneaders, rolls, Banbury mixers, etc. It can be prepared by kneading using a kneader.
〔補強層〕
　上記補強層４は、ホース全体の強度を補強するためにメッキワイヤーをブレード状、スパイラル状等に編み組してなる層である。なお、上記補強層４は、上述したように１層に限定されるものではなく、２層以上であっても差し支えない。 (Reinforcement layer)
The reinforcing layer 4 is a layer formed by braiding a plating wire into a blade shape, a spiral shape or the like in order to reinforce the strength of the entire hose. The reinforcing layer 4 is not limited to one layer as described above, and may be two or more layers.
　上記メッキワイヤーにおけるメッキ処理としては、例えば、銅メッキ、亜鉛メッキ、黄銅（銅－亜鉛系合金）メッキ、ニッケルメッキ、錫メッキ、コバルトメッキ等があげられ、好ましくは黄銅メッキである。 Examples of the plating treatment for the plating wire include copper plating, zinc plating, brass (copper-zinc alloy) plating, nickel plating, tin plating, and cobalt plating, and brass plating is preferable.
　上記メッキワイヤーの直径は、通常、０．１５～１．００ｍｍの範囲、好ましくは０．２０～０．８０ｍｍの範囲のものが用いられる。 The diameter of the plating wire is usually in the range of 0.15 to 1.00 mm, preferably in the range of 0.20 to 0.80 mm.
〔内面ゴム層〕
　上記内面ゴム層１を形成するゴムとしては、耐油性に優れたゴムが好ましく、例えば、アクリロニトリルブタジエンゴム（ＮＢＲ）、水素添加アクリロニトリルブタジエンゴム（ＨＮＢＲ）、アクリルゴム（ＡＣＭ）、エチレンアクリレートゴム（ＡＥＭ）、塩素化ポリエチレン（ＣＭ）、クロロスルホン化ポリエチレン（ＣＳＭ）、フッ素ゴム（ＦＫＭ）等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、耐油性、強度、コストの点から、ＮＢＲが好ましい。 [Inner rubber layer]
The rubber forming the inner rubber layer 1 is preferably a rubber excellent in oil resistance. For example, acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), acrylic rubber (ACM), ethylene acrylate rubber (AEM) ), Chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), fluororubber (FKM) and the like. These may be used alone or in combination of two or more. Among these, NBR is preferable from the viewpoint of oil resistance, strength, and cost.
　なお、上記内面ゴム層形成用のゴム組成物には、ＮＢＲ等のゴム以外に、補強材（カーボンブラック等）、白色充填材、可塑剤、ステアリン酸、亜鉛華、加硫剤、加硫促進剤、加工助剤等を必要に応じて適宜配合しても差し支えない。 In addition to the rubber such as NBR, the rubber composition for forming the inner rubber layer includes a reinforcing material (carbon black and the like), a white filler, a plasticizer, stearic acid, zinc white, a vulcanizing agent, and vulcanization acceleration. Agents, processing aids, etc. may be appropriately blended as necessary.
〔外面ゴム層（カバーゴム層）〕
　上記外面ゴム層５を形成するゴムとしては、耐候性に優れたゴムが好ましく、例えば、クロロプレンゴム(ＣＲ)、スチレンブタジエンゴム（ＳＢＲ）、エチレン－プロピレン－ジエン系ゴム（ＥＰＤＭ）、ＳＢＲとＥＰＤＭのブレンドゴム、ＮＢＲとＥＰＤＭのブレンドゴム、ＮＢＲと塩化ビニル（ＰＶＣ）のブレンドゴム、アクリルゴム（ＡＣＭ）、エチレンアクリレートゴム（ＡＥＭ）、塩素化ポリエチレン（ＣＭ）、クロロスルホン化ポリエチレン（ＣＳＭ）等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、耐候性、コスト、耐油性の点から、ＣＲが好ましい。 [Outer rubber layer (cover rubber layer)]
The rubber forming the outer rubber layer 5 is preferably a rubber having excellent weather resistance, such as chloroprene rubber (CR), styrene butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), SBR and EPDM. Blend rubber, blend rubber of NBR and EPDM, blend rubber of NBR and vinyl chloride (PVC), acrylic rubber (ACM), ethylene acrylate rubber (AEM), chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), etc. Is given. These may be used alone or in combination of two or more. Among these, CR is preferable from the viewpoint of weather resistance, cost, and oil resistance.
　なお、上記外面ゴム層形成用のゴム組成物には、ＣＲ等のゴム以外に、補強材（カーボンブラック等）、白色充填材、可塑剤、ステアリン酸、亜鉛華、受酸剤（高活性化マグネシウム、ハイドロタルサイト等）、老化防止剤、加硫剤、加硫剤促進剤、加工助剤等を必要に応じて適宜配合しても差し支えない。 In addition to the rubber such as CR, the rubber composition for forming the outer surface rubber layer includes a reinforcing material (carbon black, etc.), white filler, plasticizer, stearic acid, zinc white, acid acceptor (highly activated) Magnesium, hydrotalcite, etc.), anti-aging agents, vulcanizing agents, vulcanizing agent accelerators, processing aids and the like may be added as necessary.
　上記外面ゴム層５は、上記メッキワイヤーからなる補強層４に接することから、外面ゴム層形成用のゴム組成物にも、前記二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）と、モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方（Ｃ）とを併用してもよく、この場合、メッキワイヤーからなる補強層４と外面ゴム層５との接着性が向上し、ホース全体の層間接着性が向上するようになる。 Since the outer rubber layer 5 is in contact with the reinforcing layer 4 made of the plated wire, the phenolic resin (B) modified with the functional group having the double bond is also applied to the rubber composition for forming the outer rubber layer. And at least one of a vulcanizing agent having a morpholine structure and a vulcanization accelerator having a morpholine structure (C) may be used in combination. In this case, adhesion between the reinforcing layer 4 made of plated wire and the outer rubber layer 5 And the interlayer adhesion of the entire hose is improved.
〔補強糸層〕
　上記補強糸層２を形成する補強糸としては、例えば、ビニロン（ポリビニルアルコール）糸、ポリアミド（ナイロン）糸、アラミド糸、ポリエチレンテレフタレート（ＰＥＴ）糸等があげられる。これらのなかでも、高強度、高モジュラスの点から、ポリアミド糸が好ましい。 (Reinforcing thread layer)
Examples of the reinforcing yarn forming the reinforcing yarn layer 2 include vinylon (polyvinyl alcohol) yarn, polyamide (nylon) yarn, aramid yarn, polyethylene terephthalate (PET) yarn and the like. Among these, polyamide yarn is preferable from the viewpoint of high strength and high modulus.
　上記補強糸の編み組み方法としては、例えば、スパイラル編み、ブレード編み等があげられる。 Examples of the method for braiding the reinforcing yarn include spiral knitting and blade knitting.
　本発明の油圧ホースは、例えば、つぎのようにして作製することができる。すなわち、まず、押出成形機を用いて、上記内面ゴム層形成用のゴム組成物をマンドレル上に押し出して内面ゴム層１を成形する。つぎに、この内面ゴム層１の外周面に、編組機を用いて、ポリアミド糸等の補強糸をブレード状に巻き付けて補強糸層２を形成する。続いて、中間ゴム層形成用のゴム組成物を、上記補強糸層２の外周面に押し出して中間ゴム層３を形成する。つぎに、この中間ゴム層３の外周面に、黄銅メッキワイヤーをスパイラル状に編み組して補強層４を形成する。その後、上記補強層４の外周面に、上記外面ゴム層形成用のゴム組成物を押し出して外面ゴム層５を形成する。さらに、上記外面ゴム層５の外周面にポリアミド製帆布をスパイラル状に巻き付ける。最後に、この積層体を、所定の条件（例えば、１４０～１７０℃×１０～６０分間）で加硫（スチーム加硫等）し、上記ポリアミド製帆布を除去することにより、前記図１に示したような、５層構造の油圧ホースを作製することができる。 The hydraulic hose of the present invention can be manufactured, for example, as follows. That is, first, the rubber composition for forming the inner rubber layer is extruded onto a mandrel using an extruder to mold the inner rubber layer 1. Next, a reinforcing yarn layer 2 is formed on the outer peripheral surface of the inner rubber layer 1 by winding a reinforcing yarn such as polyamide yarn in a blade shape using a braiding machine. Subsequently, the intermediate rubber layer 3 is formed by extruding the rubber composition for forming the intermediate rubber layer onto the outer peripheral surface of the reinforcing yarn layer 2. Next, the reinforcing layer 4 is formed on the outer peripheral surface of the intermediate rubber layer 3 by braiding brass plating wires in a spiral shape. Thereafter, the outer rubber layer 5 is formed by extruding the rubber composition for forming the outer rubber layer on the outer peripheral surface of the reinforcing layer 4. Further, a polyamide canvas is wound around the outer peripheral surface of the outer rubber layer 5 in a spiral shape. Finally, the laminate is vulcanized (steam vulcanized, etc.) under predetermined conditions (eg, 140 to 170 ° C. × 10 to 60 minutes), and the polyamide canvas is removed, as shown in FIG. Such a five-layer hydraulic hose can be produced.
　本発明の油圧ホースは、図１に示したような５層構造に限定されるものではなく、前述したように、中間ゴム層３と補強層４とを交互に２層以上積層した構造であっても差し支えない。 The hydraulic hose of the present invention is not limited to the five-layer structure as shown in FIG. 1, but has a structure in which two or more intermediate rubber layers 3 and reinforcing layers 4 are alternately laminated as described above. There is no problem.
　本発明の油圧ホースにおいて、ホース内径は、通常、５～８５ｍｍの範囲、好ましくは６～８０ｍｍの範囲であり、ホース外径は、通常、９～１００ｍｍの範囲、好ましくは１０～８５ｍｍの範囲である。 In the hydraulic hose of the present invention, the hose inner diameter is usually in the range of 5 to 85 mm, preferably in the range of 6 to 80 mm, and the hose outer diameter is usually in the range of 9 to 100 mm, preferably in the range of 10 to 85 mm. is there.
　また、内面ゴム層１の厚みは、通常、０．７～４．０ｍｍの範囲、好ましくは１．０～３．０ｍｍの範囲、中間ゴム層３の厚みは、０．１～０．５ｍｍの範囲が好ましく、特に好ましくは０．２～０．４ｍｍの範囲であり、外面ゴム層５の厚みは、通常、０．５～２．５ｍｍの範囲、好ましくは０．８～２．０ｍｍの範囲である。 The inner rubber layer 1 has a thickness of usually 0.7 to 4.0 mm, preferably 1.0 to 3.0 mm, and the intermediate rubber layer 3 has a thickness of 0.1 to 0.5 mm. The thickness is preferably in the range of 0.2 to 0.4 mm, and the thickness of the outer rubber layer 5 is usually in the range of 0.5 to 2.5 mm, preferably in the range of 0.8 to 2.0 mm. It is.
　以下、実施例をあげて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
　まず、実施例および比較例に先立ち、中間ゴム層形成用のゴム組成物として下記に示す材料を準備した。 First, prior to Examples and Comparative Examples, the following materials were prepared as rubber compositions for forming an intermediate rubber layer.
《ジエン系ゴム（Ａ）》
〔ＮＢＲ〕
　日本ゼオン社製、ニポールＤＮ４０１（結合ニトリル量：１８％）
〔ＳＢＲ〕
　ＪＳＲ社製、ＳＢＲ１５００
〔ＮＲ〕
　ＲＳＳ＃３（ｗ２８３５０）
〔ＮＢＲ〕
　日本ゼオン社製、ニポールＤＮ３０２（結合ニトリル量：２８％）
〔ＮＢＲ〕
　日本ゼオン社製、ニポールＤＮ３３５０（結合ニトリル量：３３％） 《Diene rubber (A)》
[NBR]
Nipol DN401 (bound nitrile content: 18%), manufactured by Nippon Zeon
[SBR]
JBR, SBR1500
[NR]
RSS # 3 (w28350)
[NBR]
Nipol DN302 (bound nitrile content: 28%), manufactured by Nippon Zeon
[NBR]
Nipol DN3350 (amount of bound nitrile: 33%) manufactured by ZEON Corporation
《二重結合を有する官能基で変性されたフェノール系樹脂（Ｂ）》
〔カシューオイル変性・フェノール・ホルムアルデヒド重縮合物〕
　住友ベークライト社製、スミライトレジンＰＲ－１２６８６ << Phenolic resin modified with a functional group having a double bond (B) >>
[Cashew oil modified phenol / formaldehyde polycondensate]
Sumilite resin PR-12686, manufactured by Sumitomo Bakelite Co., Ltd.
〔アルキルフェノール樹脂〕
　日立化成社製、ヒタノール１５０１
〔アルキルフェノール・アセトアルデヒド樹脂〕
　田岡化学社製、タッキロールＥＰ－３０
〔アルキルフェノール・ホルムアルデヒド樹脂〕
　田岡化学社製、タッキロール２０１Ｇ [Alkylphenol resin]
Hitachi Chemical 1501, Hitanol 1501
[Alkylphenol acetaldehyde resin]
TAKICOL EP-30, manufactured by Taoka Chemical Co., Ltd.
[Alkylphenol / formaldehyde resin]
Made by Taoka Chemical Co., Ltd.
《モルホリン構造を有する有機加硫剤（Ｃ）》
　４，４′－ジチオジモルホリン（大内新興化学工業社製、バルノックＲ） << Organic vulcanizing agent having morpholine structure (C) >>
4,4'-dithiodimorpholine (Ouchi Shinsei Chemical Co., Ltd., Balnock R)
《モルホリン構造を有するチアゾール系加硫促進剤（Ｃ）》
　２－（４′－モルホリノジチオ）ベンゾチアゾール（大内新興化学工業社製、ノクセラーＭＤＢ） << Thiazole vulcanization accelerator having morpholine structure (C) >>
2- (4'-morpholinodithio) benzothiazole (Ouchi Shinsei Chemical Co., Ltd., Noxeller MDB)
〔グアニジン系加硫促進剤〕
　大内新興化学工業社製、ノクセラーＤ
〔チアゾール系加硫促進剤〕
　大内新興化学工業社製、ノクセラーＤＭ
〔チアゾール系加硫促進剤〕
　三新化学社製、サンセラーＭ [Guanidine vulcanization accelerator]
Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller D
[Thiazole vulcanization accelerator]
NOCELLER DM, manufactured by Ouchi Shinsei Chemical Co., Ltd.
[Thiazole vulcanization accelerator]
Sunseller M, Sanshin Chemical Co., Ltd.
〔酸化亜鉛２種〕
　三井金属鉱山社製
〔ステアリン酸〕
　花王社製、ルナックＳ３０
〔ＦＥＦ級カーボンブラック〕
　東海カーボン社製、シーストＳＯ
〔酸性シリカ〕
　東ソー・シリカ社製、ニプシールＶＮ３（ＰＨ：６．０，ＢＥＴ比表面積：２１０ｍ2／ｇ）
〔可塑剤〕
　ＡＤＥＫＡ社製、アデカサイザーＲＳ－１０７
〔アロマ系プロセスオイル〕
　新日本石油社製、コウモレックス３００
〔加硫剤〕
　硫黄（軽井沢精練所社製、硫黄） [Zinc oxide 2 types]
Made by Mitsui Metal Mining Co., Ltd. [Stearic acid]
Made by Kao, Lunac S30
[FEF grade carbon black]
SEAST SO manufactured by Tokai Carbon
[Acid silica]
NIPSEAL VN3 (PH: 6.0, BET specific surface area: 210 m 2 / g), manufactured by Tosoh Silica
[Plasticizer]
Made by ADEKA, Adeka Sizer RS-107
[Aromatic process oil]
Made by Nippon Oil Co., Ltd.
[Vulcanizing agent]
Sulfur (Sulfur manufactured by Karuizawa Seirensha)
〔実施例１～１０、比較例１～５〕
　下記の表１および表２に示す各成分を、同表に示す割合で配合し、これらを３Ｌニーダーを用いて混練して、ゴム組成物を調製した。 [Examples 1 to 10, Comparative Examples 1 to 5]
The components shown in Table 1 and Table 2 below were blended in the proportions shown in the table, and these were kneaded using a 3 L kneader to prepare a rubber composition.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　このようにして得られた実施例および比較例のゴム組成物を用いて、黄銅メッキワイヤーとの接着性を以下のようにして評価した。その結果を、上記表１および表２に示した。 Using the rubber compositions of Examples and Comparative Examples thus obtained, the adhesion with a brass-plated wire was evaluated as follows. The results are shown in Tables 1 and 2 above.
〔接着性〕
　上記で混練りした各ゴム組成物を用いて、未加硫状態のゴムシート（１００ｍｍ×１００ｍｍ、厚み２ｍｍ）を作製し、このゴムシートの上に、１本の黄銅メッキワイヤー（線径０．４ｍｍ、長さ３００ｍｍ）を置いた。これを、１５０℃×面圧２０ｋｇｆ／ｃｍ2で６０分間プレス加硫することにより、加硫接着試料を作製した（図２参照）。この加硫接着試料のゴム１１と、黄銅メッキワイヤー１２をチャックし、ＪＩＳ　Ｋ６２５６のＴ型剥離試験に準拠して、黄銅メッキワイヤー１２を矢視Ｘ方向に剥離し、黄銅メッキワイヤー１２表面におけるゴム１１の被覆率を測定した。被覆率が高いほど、ゴムと黄銅メッキワイヤーとの接着性が良好であることを示す。なお、上記黄銅メッキワイヤーとしては、トクセン社製の黄銅メッキされたワイヤー（電気メッキ、メッキ組成：Ｃｕ／Ｚｎ＝６５／３５重量％、メッキ付着量：４ｇ／ｋｇ）を使用した。 〔Adhesiveness〕
Using each rubber composition kneaded as described above, an unvulcanized rubber sheet (100 mm × 100 mm, thickness 2 mm) is prepared, and one brass-plated wire (with a wire diameter of 0.1 mm) is formed on the rubber sheet. 4 mm, length 300 mm). This was press vulcanized for 60 minutes at 150 ° C. and a surface pressure of 20 kgf / cm 2 to prepare a vulcanized adhesion sample (see FIG. 2). The rubber 11 of this vulcanized adhesion sample and the brass plating wire 12 are chucked, and the brass plating wire 12 is peeled off in the X direction in accordance with the JIS K6256 T-type peeling test, and the rubber on the surface of the brass plating wire 12 A coverage of 11 was measured. It shows that the adhesiveness of rubber | gum and a brass plating wire is so favorable that a coverage is high. The brass-plated wire used was a brass-plated wire manufactured by Toxen (electroplating, plating composition: Cu / Zn = 65/35 wt%, plating adhesion amount: 4 g / kg).
　上記表１および表２の結果から、実施例１～１０は、比較例１～５に比べて、黄銅メッキワイヤー表面のゴムの被覆率が高く、ゴムと黄銅メッキワイヤーとの接着性が良好であることがわかった。 From the results of Table 1 and Table 2, Examples 1 to 10 have higher rubber coverage on the brass plated wire surface and better adhesion between rubber and brass plated wire than Comparative Examples 1 to 5. I found out.
〔実施例１１〕
　下記の表３に示す材料からなる、１１層構造の油圧ホース（内径：１９ｍｍ）を作製した。 Example 11
An 11-layer hydraulic hose (inner diameter: 19 mm) made of the material shown in Table 3 below was produced.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、各層の材料は、以下のようにして調製した。 In addition, the material of each layer was prepared as follows.
〔内面ゴム層形成用のゴム組成物の調製〕
　ＮＢＲ（日本ゼオン社製、ニポールＤＮ２０２、結合ＡＮ量：３１％）１００重量部に、酸化亜鉛（三井金属鉱山社製、酸化亜鉛２種）５重量部、ステアリン酸（花王社製、ルナックＳ３０）１重量部、老化防止剤（精工化学社製、オゾノン３Ｃ）２重量部、老化防止剤（精工化学社製、ノンフレクックスＢＡ）２重量部、ＦＥＦ級カーボンブラック（東海カーボン社製、シーストＳＯ）９０重量部、可塑剤（ＡＤＥＫＡ社製、アデカサイザーＲＳ－１０７）１５重量部、加硫剤（軽井沢精練所社製、硫黄）２重量部、加硫剤促進剤であるテトラメチルチウラムジスルフィド（三新化学社製、サンセラーＴＴ）１．５重量部、加硫剤促進剤であるＮ－シクロヘキシル－２－ベンゾチアジルスルフェンアミド（三新化学社製、サンセラーＣＺ）１．５重量部を配合し、これらを７５Ｌニーダーで混練りし、ロールで加硫剤を混合して、ＮＢＲ系ゴム組成物を調製した。 [Preparation of rubber composition for forming inner rubber layer]
NBR (manufactured by Nippon Zeon, Nipol DN202, amount of bonded AN: 31%), 5 parts by weight of zinc oxide (Mitsui Metal Mining Co., Ltd., 2 types of zinc oxide), stearic acid (manufactured by Kao Corporation, Lunac S30) 1 part by weight, anti-aging agent (Seiko Chemical Co., Ltd., Ozonon 3C) 2 parts by weight, anti-aging agent (Seiko Chemical Co., Ltd., non-flex BA) 2 parts by weight, FEF grade carbon black (Tokai Carbon Co., Ltd., Seast SO) ) 90 parts by weight, 15 parts by weight of a plasticizer (manufactured by ADEKA, Adekasizer RS-107), 2 parts by weight of a vulcanizing agent (manufactured by Karuizawa Seirakusho Co., Ltd., sulfur), tetramethylthiuram disulfide (vulcanizing agent accelerator) Sanshin Chemical Co., Ltd., Sunseller TT) 1.5 parts by weight, vulcanizing agent accelerator N-cyclohexyl-2-benzothiazylsulfenamide (Sanshin Chemical Co., Ltd., Sunseller CZ) .5 parts by weight blended, kneaded them with 75L kneader, and mixing a vulcanizing agent in a roll to prepare a NBR rubber composition.
〔外面ゴム層形成用のゴム組成物の調製〕
　ＣＲ（電気化学工業社製、デンカクロロプレンＭ－４０、非硫黄変性タイプ）１００重量部と、補強材であるＦＥＦカーボンブラック（東海カーボン社製、シーストＳＯ）５０重量部と、白色充填材である重質炭酸カルシウム（白石カルシウム社製、ホワイトンＳＢ）２５重量部と、可塑剤である菜種油（味の素社製、菜種油）２０重量部と、ステアリン酸（花王社製、ルナックＳ３０）１重量部と、亜鉛華（三井金属社製、酸化亜鉛２種）１０重量部と、受酸剤である高活性化マグネシウム（協和化学工業社製、協和マグ♯１５０）５重量部と、受酸剤であるハイドロタルサイト〔Ｍｇ4.5 Ａｌ2 （ＯＨ）13ＣＯ3 ・３．５Ｈ2 Ｏ〕（協和化学工業社製、ＤＨＴ－４Ａ）５重量部と、老化防止剤であるＮ－フェニル－Ｎ′－イソプロピル－ｐ－フェニレンジアミン（精工化学社製、オゾノン３Ｃ）１重量部と、加硫剤である２－メルカプトイミダゾリン（三新化学社製、サンセラー２２Ｃ）０．５重量部と、加硫剤である２－メルカプトベンゾイミダゾール（大内新興化学社製、ノクラックＭＢ）０．５重量部と、加硫剤促進剤であるテトラメチルチウラムジスルフィド（三新化学社製、サンセラーＴＴ）０．５重量部とを配合し、これらを７５Ｌニーダーで混練りし、ロールで加硫剤を混合して、ＣＲ系ゴム組成物を調製した。 [Preparation of rubber composition for forming outer rubber layer]
100 parts by weight of CR (manufactured by Denki Kagaku Kogyo Co., Ltd., Denkachloroprene M-40, non-sulfur-modified type), 50 parts by weight of FEF carbon black (Shiest SO, manufactured by Tokai Carbon Co., Ltd.), and white filler 25 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium, Whiteon SB), 20 parts by weight of rapeseed oil (Ajinomoto Co., rapeseed oil) as a plasticizer, and 1 part by weight of stearic acid (manufactured by Kao Corporation, LUNAC S30) 10 parts by weight of zinc white (Mitsui Metals Co., Ltd., 2 types of zinc oxide), 5 parts by weight of highly activated magnesium (Kyowa Chemical Industry Co., Ltd., Kyowa Mag # 150) as an acid acceptor, and an acid acceptor 5 parts by weight of hydrotalcite [Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O] (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) and N-phenyl-N′-isopropyl as an anti-aging agent - -1 part by weight of phenylenediamine (manufactured by Seiko Chemical Co., Ltd., Ozonon 3C), 0.5 part by weight of 2-mercaptoimidazoline (manufactured by Sanshin Chemical Co., Ltd., Sunseller 22C), and 2- Contains 0.5 parts by weight of mercaptobenzimidazole (Nouchi MB, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 0.5 parts by weight of tetramethylthiuram disulfide (manufactured by Sanshin Chemical Co., Ltd., Sunseller TT) as a vulcanizing agent accelerator. These were kneaded with a 75 L kneader, and the vulcanizing agent was mixed with a roll to prepare a CR rubber composition.
〔油圧ホースの作製〕
　まず、押出成形機を用いて、上記内面ゴム層形成用のＮＢＲ系ゴム組成物をマンドレル上に押し出して内面ゴム層を成形した。つぎに、この内面ゴム層の外周面に、編組機を用いて、補強糸（ポリアミド糸）をブレード状に巻き付けて補強糸層を形成した。続いて、実施例６で調製した中間ゴム形成層用のゴム組成物６（表１参照）を、上記補強糸層の外周面に押し出し中間ゴム層（１）を形成した。つぎに、中間ゴム層（１）の外周面に、黄銅メッキワイヤー（直径０．４ｍｍ）をスパイラル状に編み組して補強層（１）を形成した。この作業を繰り返して、中間ゴム層（２）／補強層（２）／中間ゴム層（３）／補強層（３）／中間ゴム層（４）／補強層（４）を形成した。その後、上記補強層（４）の外周面に、上記外面ゴム層形成用のＣＲ系ゴム組成物を押し出して外面ゴム層を形成した。さらに、上記外面ゴム層の外周面に、ポリアミド製帆布をスパイラル状に巻き付けた。最後に、この積層体を、１５０℃×６０分間スチーム加硫した後、上記ポリアミド製帆布を除去して、上記表３に示した、１１層構造の油圧ホース（内径：１９ｍｍ）を作製した。 [Production of hydraulic hose]
First, using an extruder, the NBR rubber composition for forming the inner rubber layer was extruded onto a mandrel to form an inner rubber layer. Next, a reinforcing yarn layer (polyamide yarn) was wound around the outer peripheral surface of the inner rubber layer using a braiding machine to form a reinforcing yarn layer. Subsequently, the intermediate rubber layer (1) was formed by extruding the rubber composition 6 (see Table 1) for the intermediate rubber forming layer prepared in Example 6 on the outer peripheral surface of the reinforcing yarn layer. Next, on the outer peripheral surface of the intermediate rubber layer (1), a brass-plated wire (diameter 0.4 mm) was braided in a spiral shape to form a reinforcing layer (1). This operation was repeated to form an intermediate rubber layer (2) / reinforcing layer (2) / intermediate rubber layer (3) / reinforcing layer (3) / intermediate rubber layer (4) / reinforcing layer (4). Thereafter, the outer rubber layer was formed by extruding the CR rubber composition for forming the outer rubber layer on the outer peripheral surface of the reinforcing layer (4). Furthermore, a polyamide canvas was wound around the outer peripheral surface of the outer rubber layer in a spiral shape. Finally, the laminate was steam vulcanized at 150 ° C. for 60 minutes, and then the polyamide canvas was removed to produce an 11-layer hydraulic hose (inner diameter: 19 mm) shown in Table 3 above.
　なお、黄銅メッキワイヤーとしては、トクセン社製の黄銅メッキされたワイヤー（電気メッキ、メッキ組成：Ｃｕ／Ｚｎ＝６５／３５重量％、メッキ付着量：４ｇ／ｋｇ）を使用した。 In addition, the brass plating wire (electroplating, plating composition: Cu / Zn = 65/35 weight%, plating adhesion amount: 4 g / kg) by Toxen Co., Ltd. was used as a brass plating wire.
〔実施例１２〕
　下記の表４に示すように、中間ゴム層形成用のゴム組成物を、実施例６のゴム組成物に代えて、実施例７のゴム組成物（表１参照）に変更した以外は、実施例１１と同様にして、１１層構造の油圧ホースを作製した。 Example 12
As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Example 7 (see Table 1) in place of the rubber composition of Example 6, and this was carried out. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
〔実施例１３〕
　下記の表４に示すように、中間ゴム層形成用のゴム組成物を、実施例６のゴム組成物に代えて、実施例１０のゴム組成物（表１参照）に変更した以外は、実施例１１と同様にして、１１層構造の油圧ホースを作製した。 Example 13
As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Example 10 (see Table 1) in place of the rubber composition of Example 6, and this was carried out. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
〔比較例６〕
　下記の表４に示すように、中間ゴム層形成用のゴム組成物を、実施例６のゴム組成物に代えて、比較例２のゴム組成物（表２参照）に変更した以外は、実施例１１と同様にして、１１層構造の油圧ホースを作製した。 [Comparative Example 6]
As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Comparative Example 2 (see Table 2) instead of the rubber composition of Example 6. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
〔比較例７〕
　下記の表４に示すように、中間ゴム層形成用のゴム組成物を、実施例６のゴム組成物に代えて、比較例３のゴム組成物（表２参照）に変更した以外は、実施例１１と同様にして、１１層構造の油圧ホースを作製した。 [Comparative Example 7]
As shown in Table 4 below, the rubber composition for forming the intermediate rubber layer was replaced with the rubber composition of Comparative Example 3 (see Table 2) in place of the rubber composition of Example 6, and this was carried out. In the same manner as in Example 11, an 11-layer hydraulic hose was produced.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　このようにして得られた実施例１１～１３および比較例６，７の油圧ホースを用い、下記の基準に従って、インパルス耐久性の評価を行った。その結果を、上記表４に示した。 Using the hydraulic hoses of Examples 11 to 13 and Comparative Examples 6 and 7 obtained as described above, impulse durability was evaluated according to the following criteria. The results are shown in Table 4 above.
〔インパルス耐久性〕
　ＪＩＳ　Ｋ６３３０－８（グレードＢ）に準拠し、下記の条件にて、インパルス耐久試験機（カヤバシステムマシナリー社製）を用いて、インパルス耐久性の評価を行った。なお、加圧状態で０．５秒、無加圧状態で０．５秒を１サイクルとした。
　試験液：作動油
　温度：１００℃
　圧力：３５ＭＰａ
　ホースの取付形状：１８０°曲げ
　インパルス圧力の周波数：１Ｈｚ [Impulse durability]
In accordance with JIS K6330-8 (grade B), impulse durability was evaluated using an impulse durability tester (manufactured by Kayaba System Machinery) under the following conditions. One cycle was 0.5 second in the pressurized state and 0.5 second in the non-pressurized state.
Test fluid: hydraulic oil Temperature: 100 ° C
Pressure: 35MPa
Hose mounting shape: 180 ° bending Impulse pressure frequency: 1 Hz
　上記表４の結果から、実施例１１～１３は、インパルスサイクル数５０万回でもホースの異常がなかった。 From the results of Table 4 above, in Examples 11 to 13, there was no abnormality in the hose even when the number of impulse cycles was 500,000.
　これに対して、比較例６は、インパルスサイクル数３万回でホース抜けが生じた。また、比較例７は、インパルスサイクル数５万回でホース抜けが生じた。
　このことから、実施例の油圧ホースは、比較例の油圧ホースに比べて、インパルス耐久性が優れていることがわかった。 On the other hand, in Comparative Example 6, the hose disconnection occurred at the number of impulse cycles of 30,000. Further, in Comparative Example 7, the hose was disconnected at the number of impulse cycles of 50,000.
From this, it was found that the hydraulic hose of the example was superior in the impulse durability as compared with the hydraulic hose of the comparative example.
　なお、上記実施例においては、本発明における具体的な形態について示したが、上記実施例は単なる例示にすぎず、限定的に解釈されるものではない。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。 In addition, although the specific form in this invention was shown in the said Example, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.
　本発明の高圧油圧ホースは、耐圧性が要求されるホース全般に使用可能であるが、例えば、建機、マイニング機械、産業車両（フォークリフト、無人搬送車等）等に使用でき、特に建機やマイニング機械向けの高圧油圧ホースとして好適に用いられる。 The high-pressure hydraulic hose of the present invention can be used for all hoses that require pressure resistance. For example, it can be used for construction equipment, mining machinery, industrial vehicles (forklifts, automatic guided vehicles, etc.), It is suitably used as a high-pressure hydraulic hose for mining machines.

Claims (4)

  1. 　流体を通す内面ゴム層と、その外側に位置するメッキワイヤーからなる補強層と、この補強層に接するゴム層とを有する高圧油圧ホースであって、上記ゴム層が、下記の（Ａ）～（Ｃ）を含有するゴム組成物からなることを特徴とする高圧油圧ホース。
    （Ａ）ジエン系ゴム。
    （Ｂ）二重結合を有する官能基で変性されたフェノール系樹脂。
    （Ｃ）モルホリン構造を有する加硫剤およびモルホリン構造を有する加硫促進剤の少なくとも一方。     A high-pressure hydraulic hose having an inner surface rubber layer through which a fluid passes, a reinforcing layer made of a plated wire located outside thereof, and a rubber layer in contact with the reinforcing layer, wherein the rubber layer includes the following (A) to (A A high-pressure hydraulic hose comprising a rubber composition containing C).
    (A) Diene rubber.
    (B) A phenolic resin modified with a functional group having a double bond.
    (C) At least one of a vulcanizing agent having a morpholine structure and a vulcanization accelerator having a morpholine structure.
  2. 　（Ｂ）がカシュー変性フェノール系樹脂である請求項１記載の高圧油圧ホース。 The high pressure hydraulic hose according to claim 1, wherein (B) is a cashew-modified phenolic resin.
  3. 　（Ｃ）がモルホリン構造を有するチアゾール系加硫促進剤である請求項１または２記載の高圧油圧ホース。 The high pressure hydraulic hose according to claim 1 or 2, wherein (C) is a thiazole vulcanization accelerator having a morpholine structure.
  4. 　内面ゴム層の外周面に補強糸層、中間ゴム層、メッキワイヤーからなる補強層、外面ゴム層が順次形成されてなり、上記中間ゴム層が、上記（Ａ）～（Ｃ）を含有するゴム組成物からなる請求項１～３のいずれか一項に記載の高圧油圧ホース。 A rubber containing a reinforcing yarn layer, an intermediate rubber layer, a reinforcing layer made of plated wire, and an outer rubber layer are formed in order on the outer peripheral surface of the inner rubber layer, and the intermediate rubber layer contains the rubbers (A) to (C). The high-pressure hydraulic hose according to any one of claims 1 to 3, comprising the composition.
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