JP6052040B2 - Rubber composition metal laminate, vulcanized rubber product, and method for producing vulcanized rubber product - Google Patents

Description

The present invention, rubber compositions metal laminate, vulcanized rubber products, and to a process for the production of vulcanized rubber products.

Hydraulic hoses and high-pressure hoses (hereinafter collectively referred to as hydraulic hoses, etc.) used for various industrial applications function as hoses without causing liquid leakage even in harsh environments with large temperature and pressure fluctuation ranges. There is known a structure in which a reinforcing layer braided with a reinforcing thread, a steel wire or the like is provided between the rubber layer and the rubber layer so as to maintain the same.
Such a reinforcing layer is used, for example, by plating the surface with a metal such as brass (brass) in order to enhance the adhesion to the rubber layer.

  Patent Document 1 describes a rubber composition in which a rubber component and a porous inorganic filler are blended and moisture is released during vulcanization to improve the adhesion between the brass-plated reinforcing layer and the rubber layer. ing.

JP 2002-13083 A

  However, in the rubber composition described in Patent Document 1, the moisture necessary for vulcanization cannot be retained by moisture evaporation during long-term storage, and as a result, there is a problem in that the adhesion between the rubber layer and the reinforcing layer is lowered. is there. In particular, when vulcanizing by the oven vulcanization method, which is a continuous vulcanization method, in order to improve productivity, the evaporation of moisture is remarkable during vulcanization, and sufficient adhesion between the rubber layer and the reinforcing layer cannot be obtained. There is a problem.

  Therefore, the appearance of a rubber composition having good adhesion to a metal-plated reinforcing layer is eagerly desired.

The present invention relates to a rubber composition metal laminate comprising a rubber composition having good adhesion to a metal-plated reinforcing layer and a reinforcing layer, a vulcanized rubber product obtained by vulcanizing such a rubber composition metal laminate, Another object of the present invention is to provide a method for producing a vulcanized rubber product.

The present invention provides the following (1) to ( 12 ).
(1) For 100 parts by mass of the sulfur vulcanizable diene polymer,
3.0 parts by weight or more and 15 parts by weight or less of water;
0.5 to 10 parts by mass of a water absorbent resin,
A rubber layer made of a metal surface adhesive rubber composition comprising:
A rubber composition metal laminate in which a reinforcing layer having a metal surface is laminated.

(2) The rubber composition metal laminate according to (1), wherein the metal surface is a brass-plated metal surface.

(3) The water-absorbent resin according to (1) or (2), wherein the water-absorbent resin is at least one selected from an acrylic acid polymer partial sodium salt crosslinked product, a modified acrylic crosslinked polymer, and a polyether compound. Rubber composition metal laminate .

(4) The rubber composition metal laminate according to (3), wherein the polyether compound is polyethylene oxide or polyethylene glycol.

(5) The diene polymer is natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber ( The rubber composition metal laminate according to any one of the above (1) to (4), comprising at least one selected from CR).

(6) The rubber composition metal laminate according to any one of (1) to (5) , further comprising a vulcanizing agent.

( 7 ) The rubber composition metal laminate according to any one of (1) to (6), wherein the metal surface is a brass-plated metal surface.

( 8 ) The rubber composition metal laminate according to any one of (1) to (7), wherein the reinforcing layer has a braided (blade) structure in which wires are knitted or a spiral structure.

( 9 ) Vulcanization in which the rubber layer of the rubber composition metal laminate according to any one of ( 1 ) to ( 8 ) is vulcanized in the presence of a sulfur-containing vulcanizing agent and adhered to the reinforcing layer Rubber product.

( 10 ) The vulcanized rubber product according to the above ( 9 ), which is a hydraulic hose or a high-pressure hose.

( 11 ) The vulcanized rubber product according to ( 10 ), wherein the hydraulic hose or the high-pressure hose is vulcanized by passing through an oven vulcanizer.

( 12 ) a laminating step of laminating a reinforcing layer having a surface plated with brass and at least one rubber layer to produce a laminate;
Passing through the laminate in an oven vulcanizer, vulcanizing the rubber layer, and bonding to the brass plated reinforcing layer,
The rubber layer is
For 100 parts by mass of the sulfur vulcanizable diene polymer,
3 . 0 parts by weight or more and 15 parts by weight or less of water;
0.5 to 10 parts by mass of a water absorbent resin,
A rubber composition comprising:
A method for producing a vulcanized rubber product, further comprising a sulfur-containing vulcanizing agent.

According to the present invention, a rubber composition having good adhesion to a metal-plated reinforcing layer, a rubber composition metal laminate of such a rubber composition and a reinforcing layer, and such a rubber composition metal laminate. It is possible to provide a vulcanized product obtained by vulcanizing the vulcanized product and a method for producing the vulcanized product.
The present invention is suitable for hose applications continuously produced by an oven vulcanization method.

FIG. 1 is a partially cutaway perspective view showing a configuration example of a hydraulic hose as a vulcanized rubber product. FIG. 2 is a process diagram showing an example of manufacturing a hydraulic hose as a vulcanized rubber product. FIG. 3 is a schematic diagram illustrating details of the vulcanization process in FIG. 2. FIG. 4 is a partial cross-sectional view showing an example of a layer structure around a mandrel fed into the vulcanizer in FIG.

  Hereinafter, the present invention will be described in detail. In addition, this invention is not limited by the content described in the following embodiment and an Example. In addition, constituent elements in the embodiments and examples described below include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the embodiments and examples described below may be appropriately combined or may be appropriately selected and used.

[Rubber composition]
Hereinafter, the rubber composition according to this embodiment will be described. The rubber composition according to the present embodiment is a rubber composition that adheres to a brass-plated wire reinforcing layer, and is 1.0 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of a sulfur vulcanizable diene polymer. And 0.5 to 10 parts by mass of a water-absorbent resin. Hereinafter, each component constituting the rubber composition will be described.

<Diene polymer>
Diene polymers capable of sulfur vulcanization include natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), and chloroprene rubber. One or more polymers selected from (CR).

  Here, sulfur vulcanizable means the property that a crosslinked structure is formed through sulfur. Sulfur is provided by a vulcanizing agent, which will be described later.

  The rubber composition according to the present embodiment preferably contains the sulfur vulcanizable diene polymer in an amount of 20% by mass to 70% by mass with respect to the entire rubber composition. Within this range, good rubber mixing processability and rubber appearance can be obtained.

<Water>
The water may be tap water or purified water such as distilled water, ion exchange water, filtered water. Moreover, the water | moisture content adsorb | sucked to the filler (for example, carbon black) may be sufficient. The blending amount of water is 1.0 part by mass or more and 15 parts by mass or less, and more preferably 3.0 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the diene polymer. In this range, by blending in the composition together with the water-absorbing resin described later, it is possible to stably maintain a suitable amount of moisture in the composition even during long-term storage until vulcanization, and an oven with large moisture evaporation. Even in hose production by continuous production using a vulcanization method, it is possible to maintain good adhesion between the rubber layer and the reinforcing layer.

<Water absorbent resin>
The water absorbent resin has a function of stably holding water in the rubber composition (compound). Generally, a water-absorbing resin refers to a resin that exhibits a water absorption amount of 10 g or more per 1 g of resin. For example, the water-absorbent resin is preferably a porous material having high hydrophilicity and a three-dimensional network structure that can take water into pores (pores). Specifically, acrylic acid polymer partial sodium salt cross-linked products, modified acrylic cross-linked polymers, polyether compounds and the like can be mentioned. It is preferable to select at least one water-absorbing resin from the above compound group. Two or more kinds may be used in combination.

  Examples of the acrylic acid polymer partial sodium salt cross-linked product include trade names “AQUALIC CA”, ACRYAC, Nippon Shokubai Co., Ltd., and the like.

  Examples of the modified acrylic crosslinked polymer include trade name “AQUALIC CS”, manufactured by Nippon Shokubai Co., Ltd.

  Examples of the polyether compound include polyethylene oxide and polyethylene glycol.

  The blending amount of the water absorbent resin is 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 3.0 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the diene polymer. In this range, by blending in the composition together with the above-mentioned water, it is possible to stably maintain an appropriate amount of moisture in the composition even during long-term storage until vulcanization, and oven vulcanization with large moisture evaporation. The adhesiveness between the rubber layer and the reinforcing layer can be kept good even in hose production by continuous production by the method. In addition, when there is too much compounding quantity of a water absorbing resin, since the rubber | gum external appearance worsens due to the height of the water absorbing property, it is preferable to use in the said range.

<Vulcanizing agent>
The rubber composition is preferably vulcanized in the presence of sulfur, and preferably further blended with a sulfur-containing vulcanizing agent. Examples of the sulfur-containing vulcanizing agent include sulfur, tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide (TETD), tetrabutyl thiuram disulfide (TBTD), dipentamethylene thiuram tetrasulfide (DPTT), tetrabenzyl thiuram disulfide, Examples thereof include organic sulfur-containing compounds such as dimorpholine disulfide and alkylphenol disulfide. Examples of sulfur include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur and the like.

  As the vulcanizing agent, the following non-sulfur vulcanizing agent may be further blended. Examples of the non-sulfur vulcanizing agent include vulcanizing agents such as organic peroxides, metal oxides, phenol resins, and quinone dioximes.

  Examples of the organic peroxide vulcanizing agent include dicumyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like.

  Examples of other vulcanizing agents include resins such as zinc white, magnesium oxide, phenol resin, p-quinone dioxime, p-dibenzoylquinone dioxime, poly-p-dinitrosobenzene, methylene dianiline, and the like. be able to.

  The rubber composition of the present invention preferably further contains a vulcanization accelerator. Examples of the vulcanization accelerator include an aldehyde-ammonia vulcanization accelerator, an aldehyde-amine vulcanization accelerator, a thiourea vulcanization accelerator, a guanidine vulcanization accelerator, a thiazole vulcanization accelerator, and sulfene. Examples include amide vulcanization accelerators, thiuram vulcanization accelerators, dithiocarbamate vulcanization accelerators, and xanthate vulcanization accelerators. These may be used alone or in combination of two or more.

[Other additives]
Moreover, the rubber composition can contain other additives as required within the range not impairing the object of the present invention. Other additives include, for example, fillers, plasticizers, softeners, anti-aging agents, organic activators, antioxidants, antistatic agents, flame retardants, crosslinking accelerators, vulcanization retarders, adhesion promoters. An agent can be mentioned.

  Examples of the filler include carbon black, silica (white carbon), clay, talc, iron oxide, zinc oxide (ZnO), titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium sulfate, mica. (Mica) and diatomaceous earth. These may be used alone or in combination of two or more. As carbon black, it can select and use suitably according to a use, and in one suitable form, ISAF, FEF, etc. can be used, for example. The silica is not particularly limited, and examples thereof include crystalline silica, precipitated silica, amorphous silica (for example, high-temperature treated silica), fumed silica, calcined silica, precipitated silica, pulverized silica, and fused silica. In particular, silica is known to produce carbon gel (bound rubber) like carbon black, and can be suitably used as necessary. Examples of the clay include wax stone clay, kaolin clay, and calcined clay.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, Examples thereof include trioctyl phosphate, trimellitic acid ester, propylene glycol adipate polyester, butylene glycol adipate polyester, and naphthene oil. These may be used alone or in combination of two or more.

  Specific examples of the softener include aroma oils, naphthenic oils, paraffin oils, petroleum resins, vegetable oils, liquid rubbers, etc., and these may be used alone or in combination of two or more. May be.

  Examples of the antioxidant include N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6PPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), and N-isopropyl. -N'-phenyl-p-phenylenediamine (IPPD), styrenated phenol (SP), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), etc., and these may be used alone. Two or more types may be used in combination.

  Specific examples of the organic activator include stearic acid, oleic acid, lauric acid, and zinc stearate. These may be used alone or in combination of two or more.

  Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether. Examples of the non-halogen flame retardant include aluminum hydroxide, magnesium hydroxide, tricresyl phosphate, and diphenyl cresyl phosphate.

  As the crosslinking accelerating aid, general rubber auxiliaries can be used together. For example, zinc white; stearic acid, oleic acid, and Zn salts thereof can be used.

  Examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid, salicylic acid, and acetylsalicylic acid; N-nitroso-diphenylamine, N-nitroso-phenyl-β-naphthylamine, Nitroso compounds such as coalescence; halides such as trichloromelanin; 2-mercaptobenzimidazole, N- (cyclohexylthio) phthalimide (PVI) and the like. These may be used alone or in combination of two or more.

  Adhesion aids are triazine thiol compounds (for example, 2,4,6-trimercapto-1,3,5-triazine, 6-butylamino-2,4-dimercapto-1,3,5-triazine), resorcin , Cresol, resorcin-formalin latex, monomethylolmelamine, monomethylolurea, ethylene maleimi, cobalt naphthenate, cobalt stearate, cobalt versatate, cobalt dodecanoate, etc., and one or more of these are used. be able to.

  Each of the various additives described above may be used alone or in combination of two or more.

<Method for producing rubber composition>
The method for producing the rubber composition of the present invention is not particularly limited, and a conventionally known method can be used. A diene polymer, water, and a water-absorbing resin can be added as necessary with a vulcanizing agent or the like. It can manufacture by mix | blending with another additive. For example, it can be produced by kneading the diene polymer, water, a water-absorbing resin, and, if necessary, a vulcanizing agent and other additives with a Banbury mixer, a kneader or the like.

[Rubber composition metal laminate]
The rubber composition metal laminate in the present embodiment is configured as a laminate of the rubber composition and a wire reinforcing layer whose surface is metal-plated. FIG. 1 shows a basic structure when the rubber composition metal laminate is embodied as a hose. As shown in FIG. 1, the hose 1 includes an inner rubber layer 2 through which fluid passes, a reinforcing layer 3 provided around the outer side of the inner rubber layer 2, and an outer rubber provided around the outer side of the reinforcing layer 3. Layer 4. One or both of the inner rubber layer 2 and the outer rubber layer 4 are rubber layers made of the composition according to the present embodiment, and the reinforcing layer 3 is a wire blade woven with a steel wire, The surface is brass plated. The reinforcing layer 3 is disposed so as to be sandwiched between the inner rubber layer 2 and the outer rubber layer 4, and the inner rubber layer 2, the reinforcing layer 3, and the outer rubber layer are obtained by vulcanization of the rubber layers 2 and 4. 4 is bonded and fixed.

<Rubber layer>
Either one or both of the inner rubber layer 2 and the outer rubber layer 4 are composed of the rubber composition according to this embodiment. From the viewpoint of weather resistance of the hose, it is preferable to form at least the outer rubber layer 4 using the rubber composition of the present invention.

  In the present invention, the thickness of the inner rubber layer 2 is preferably, for example, 0.2 mm or more and 4.0 mm or less, and more preferably 0.5 mm or more and 2.0 mm or less. Similarly, the thickness of the outer rubber layer 4 is preferably 0.2 mm to 4.0 mm, for example, and more preferably 0.5 mm to 2.0 mm.

<Reinforcing layer>
The reinforcing layer 3 is a layer provided between the inner rubber layer 2 and the outer rubber layer 4 from the viewpoint of maintaining strength. In the present embodiment, the reinforcing layer 3 is formed by a wire blade formed by braiding a steel wire rod.

  In addition to the wire blade, the reinforcing layer 3 may be formed as a spiral wire in which a steel wire rod is spirally wound around the inner rubber layer 2. The material forming the reinforcing layer and the knitting method, weaving method, or winding method can be appropriately selected depending on the application, for example, depending on the pressure resistance. In a hydraulic hose or the like, it is preferable to form a reinforcing layer with a wire blade.

  The reinforcing layer 3 is metal-plated on the surface in order to enhance the adhesion with the rubber layer. In metal plating, brass coating is applied to piano wire and hard steel wire. Copper is plated on the steel wire and zinc is plated on the copper. A heat diffusion treatment is applied to form a brass coating.

[Vulcanized rubber products]
The rubber composition metal laminate of the rubber composition and the reinforcing layer 3 is crosslinked, that is, vulcanized in the presence of a sulfur-containing vulcanizing agent, so that the molecules forming the rubber layers 2 and 4 are crosslinked by sulfur. The rubber layers 2 and 4 are given elasticity and tensile strength, and the metal (copper, zinc) and sulfur constituting the brass plating at the interface with the reinforcement layer 3 are combined with the rubber layers 2 and 4 and the reinforcement layer. 3 are bonded together.

  The sulfur-containing vulcanizing agent is preferably blended with other materials when forming a compound as a rubber composition, but the molecular chain forming the diene polymer with sulfur is cross-linked with sulfur, and the rubber As long as the rubber layers 2, 4 and the reinforcing layer 3 are bonded to each other by bonding of metal (copper, zinc) and sulfur at the interface between the layers 2, 4 and the reinforcing layer 3, the compounding is limited to the compound preparation. Not.

  As the vulcanization method, a method of heating the rubber composition at a predetermined temperature for a predetermined time in the presence of a sulfur-containing vulcanizing agent can be employed. At this time, the vulcanization temperature is preferably 130 ° C. or higher and 180 ° C. or lower. The vulcanization time is preferably from 30 minutes to 240 minutes. By combining the temperature and time within this range, desired physical properties of the vulcanized rubber product, such as elasticity, tensile strength, appearance, adhesion at the rubber-metal interface, and rubber attachment at the rubber-metal interface can be obtained.

  The vulcanized rubber product in the present embodiment is suitable as a hydraulic hose or the like. As a method of manufacturing a hydraulic hose, etc., there are a steam vulcanization method in which a rubber composition metal laminate is enclosed in a high pressure vessel and crosslinked in a steam can, and the rubber composition metal laminate is surrounded by a nylon cloth or the like And an oven vulcanization method for vulcanizing in a hot air drying furnace. Typically, the steam vulcanization method is a batch process, and the oven vulcanization method is a continuous process. In hose manufacture, it is preferable to employ an oven vulcanization method which is a continuous process.

[Method of manufacturing vulcanized rubber products]
Below, the method to manufacture the vulcanized rubber product which concerns on this embodiment is demonstrated. Here, a case where a hydraulic hose is manufactured as a vulcanized rubber product will be described as an example. FIG. 1 is a partially broken perspective view showing an example of a hydraulic hose according to the present embodiment. FIG. 2 is a process diagram showing an example of a hydraulic hose manufacturing apparatus.

<Manufacture of hydraulic hoses>
As shown in FIG. 1, the hydraulic hose 1 has a structure in which a reinforcing layer 3 and an outer rubber layer 4 are sequentially laminated on the outer peripheral surface of the inner rubber layer 2. In the illustrated example, the reinforcing layer 3 is a single layer, but a plurality of reinforcing layers 3 in which an intermediate rubber layer is disposed between the layers may be provided. Further, at least one of the inner rubber layer 2 and the outer rubber layer 4, preferably the outer rubber layer 4, is formed of the rubber composition of the present invention. The inner rubber layer 2 is preferably a rubber composition mainly composed of acrylonitrile butadiene rubber (NBR) having excellent oil resistance.

  A method for manufacturing a hydraulic hose according to the present embodiment will be described below with reference to FIGS. 2 and 3.

<Hose manufacturing process>
Generally, the rubber hose is an extrusion process (step S101) of a rubber material for forming the inner rubber layer 2 on the outer peripheral surface of the mandrel 6 shown in FIG. 2, a knitting process of the reinforcing layer 3 (step S102), and an extrusion / addition of the outer rubber layer 4. It is obtained by the sulfur process (step S103) and the mandrel 6 extraction process (step S104), and then is packed and shipped through a hydraulic pressure inspection and an inspection winding process.

  First, as shown in FIG. 2, in step S <b> 101, a hose 6 </ b> A in which an unvulcanized inner rubber layer 2 is coated on the outer peripheral surface of the mandrel 6 fed out from the unwinder 5 by the first extruder 7 is wound up. Take up the machine 8.

  Next, in step S102, the hose 6B, which is braided by the braiding machine 9 to form the reinforcing layer 3 so as to cover the inner rubber layer 2 constituting the hose 6A fed out from the winding and unwinding machine 8, is unwound and unwound. Wind up on machine 10. A metal wire is used for the cord of the reinforcing layer 3. For the metal wire, a steel wire plated with brass is used in order to improve the adhesion to rubber. The reinforcing layer 3 may be formed by spirally winding a metal wire around the inner rubber layer 2 formed around the mandrel 6.

  Next, in step S103, the unvulcanized outer rubber layer 4 is covered with the second extruder 11 on the reinforcing layer 3 of the hose 6B fed out from the winding unwinder 10 to form a hose body 6C. The hose body 6 </ b> C is wound around the winder 16. In the present embodiment, while the hose body 6C exits the second extruder 11 and is wound around the winder 16, the vulcanizing device 14 is installed, and the vulcanized hose 6E is wound around the winder 16. However, the vulcanization step may be provided after the hose body 6C is wound up by the winder 16. Further, before and after the vulcanizing device 14, a wrapping device 13 and an unwrapping device 15 for detaching a protective cloth such as a nylon cloth from the hose body 6C are provided. In FIG. 2, the hose before vulcanization in which the nylon cloth is wound by the wrapping device 13 is indicated by reference numeral 6D, and the hose after vulcanization and before removing the nylon cloth is indicated by reference numeral 6E. The vulcanization process will be described later.

  Next, in step S104, after vulcanization, the mandrel 6 is extracted from the unwrapped hose 6F by the mandrel extraction device 17 to complete the hose 6G.

<Vulcanization process>
FIG. 3 is a schematic diagram for explaining the vulcanization process using the vulcanizer 14 in more detail in step S103 of FIG.

  As shown in FIG. 3, the nylon cloth 18 is wound around the hose body 6 </ b> C exiting the second extruder 11 by the lapping device 13. The hose body 6 </ b> C surrounded by the nylon cloth 18 is carried into the vulcanizer 14. The vulcanizing device 14 is a hot air circulation type continuous vulcanizing device that advances vulcanization with hot air 19. This vulcanization method is also referred to as an oven vulcanization method.

  FIG. 4 is a partial cross-sectional view for explaining an example of the layer structure around the mandrel 6 to be charged into the vulcanizer. As shown in FIG. 4, the inner rubber layer 2 is formed around the mandrel 6, the reinforcing layer 3 is further formed around the inner rubber layer 2, and the outer rubber layer 4 is further formed around the inner rubber layer 4. A nylon cloth 18 is wound around the outer rubber layer 4 and heated in this state to proceed with the vulcanization process.

As described above, the vulcanization temperature is preferably 130 ° C. or more and 180 ° C. or less, and the vulcanization time, that is, the vulcanization time in the vulcanizer 14 is preferably 30 minutes or more and 240 minutes or less. In this temperature range and vulcanization time, a hydraulic hose with good adhesion between the rubber layer and the reinforcing layer can be obtained.
<Rubber composition>
Either one or both of the inner rubber layer 2 and the outer rubber layer 4 is preferably composed of the rubber composition according to the present invention. By using the rubber composition according to the present invention, it is possible to manufacture a hydraulic hose having good adhesion to a metal reinforcing layer.

  According to the rubber composition according to the present invention, moderate moisture can be stably held in the composition until immediately before vulcanization. Therefore, even in an oven vulcanization method with large moisture evaporation, adhesion failure and adhesion due to lack of moisture. Can be suppressed. However, it goes without saying that the rubber composition according to the present invention can be suitably used for the production of rubber products by other conventionally known vulcanization methods. Examples of other vulcanization methods include press vulcanization, steam vulcanization, and hot water vulcanization.

  Moreover, in the said embodiment, although the manufacturing process by a continuous processing system was illustrated, the vulcanized rubber product concerning this invention can be manufactured also by the method of bonding after manufacturing a rubber layer and a reinforcement layer by another process.

  The field of use of the hydraulic hose manufactured by the manufacturing method according to the present embodiment is not particularly limited and can be applied to various uses. For example, an air conditioner hose for a car, a power steering hose, and a hydraulic pressure for a construction vehicle It can be suitably used as a hydraulic hose used in a system or the like.

  Further, in the present embodiment, the rubber composition metal laminate and the vulcanized rubber product have been described using a hydraulic hose, but the present invention is not limited to this, and other rubber laminates such as a conveyor belt, for example. Can be used in the same manner.

  As described above, according to the rubber composition metal laminate, the vulcanized rubber product, and the method for producing the vulcanized rubber product of the present invention, the rubber layer and the reinforcing layer can be used even in the continuous production method using the oven vulcanization method. A vulcanized rubber product with good adhesion can be provided. In particular, even when used after long-term storage in a dry state, it is possible to provide a composition that forms a rubber product having good adhesion to the reinforcing layer. This vulcanized rubber product can be suitably used for hydraulic hoses, high-pressure hoses and the like.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.

<1. Preparation of rubber composition>
(Examples 1 to 9 )
The raw material compounding ratio shown in Table 1 were kneaded in a Banbury Kimi Sir, a rubber composition was obtained according to Example 1-9. In addition, the unit of the numerical value in a table | surface is represented by the mass part when the total mass of a diene polymer is set to 100 except the case where there is particular notice.

(Comparative Examples 1 to 9 )
The raw materials having the compounding ratios shown in Tables 1 and 2 were kneaded with a Banbury Kimiser to obtain rubber compositions according to Comparative Examples 1 to 9 . In addition, the unit of the numerical value in a table | surface is represented by the mass part when the total mass of a diene polymer is set to 100 except the case where there is particular notice.

The detail of each component described in Table 1 and Table 2 is as follows.
NBR: trade name “Nancar 3345”, manufactured by Nanteru Chemical Industry Co., Ltd., acrylonitrile content: 34% by mass, Mooney viscosity (ML1 + 4, 100 ° C.) 45
EPDM: Trade name “EPT 4070”, manufactured by Mitsui Chemicals, ethylene content 56 mass%, ethylidene norbornene content 8 mass%, Mooney viscosity (ML1 + 4, 125 ° C.) 47
SBR: trade name “Nipol 1502”, manufactured by Nippon Zeon Co., Ltd., emulsion polymerization SBR, bound styrene content 23.5 mass%, Mooney viscosity (ML1 + 4, 100 ° C.) 52
CR: Trade name “Denka Chloroprene S-41”, manufactured by Denki Kagaku Kogyo Co., Ltd., non-sulfur modified chloroprene rubber, Mooney viscosity (ML1 + 4, 100 ° C.) 48
Water-absorbing resin 1: Acrylic acid polymer sodium neutralized salt cross-linked product, trade name “Aquaric CA-K4”, manufactured by Nippon Shokubai Co., Ltd. Water-absorbing resin 2: Modified acrylic cross-linked polymer, trade name “Aquaric CS” -6S ", Nippon Shokubai Co., Ltd., water-absorbing resin 3: Polyalkylene oxide, trade name" Aqua Coke TW ", Sumitomo Seika Co., Ltd., water-absorbing resin 4: polyethylene glycol, trade name" Macrogol 6000P ", Sanyo Chemical -Water: Tap water-Sulfur: Hosoi Chemical Co., Ltd.-Vulcanization accelerator 1: Nt-Butylbenzothiazole-2-sulfenamide, trade name "Noxeller NS-P", Ouchi Shinsei Chemical Industry Company-made vulcanization accelerator 2: Tetramethylthiuram monosulfide, trade name "Sunseller TS-G", Sanshin Chemical Industry Co., Ltd., vulcanization accelerator 3: Diphenylguanidine, trade name "Sokushino DG ”, manufactured by Sumitomo Chemical Co., Ltd., Scorch inhibitor: N-cyclohexylthiophthalimide, manufactured by FLEXSYS, ISAF grade carbon black: trade name“ Show Black N220 ”, manufactured by Showa Cabot Corporation, FEF grade carbon black: trade name “HTC # 100”, manufactured by Shin-Nikka Carbon Co., Ltd., hard clay: trade name “Suprex Clay”, manufactured by Kentucky Tennessee Clay Company, Inc., zinc oxide 3 types: manufactured by Shodo Chemical Co., Ltd., magnesium oxide: trade name “Kyowa Mag 150 "Kyowa Chemical Industry Co., Ltd., stearic acid: manufactured by Nippon Oil & Fats Co., Ltd./Ozone degradation inhibitor: Trade name" Ozone Non 6C ", Seiko Chemical Co., Ltd., plasticizer: Dioctyl adipate, trade name" DIACIZER DOA " Product / Process oil: Aroma-based oil, trade name “A-OMIX”, Made by Sankyo Oil Chemical Co., Ltd.

<2. Evaluation of rubber composition>
Using each rubber composition obtained in Examples 1 to 9 and Comparative Examples 1 to 9 as an outer rubber layer, it was adhered to a reinforcing layer prepared with a brass-plated wire blade, and a hose-shaped test piece was formed as follows. Produced.

  First, a wire having a surface plated with brass was wound around a mandrel having an outer diameter of 34 mm in a blade shape to form a reinforcing layer. Subsequently, an unvulcanized sheet having a thickness of 2.5 mm prepared from each of the obtained rubber compositions was bonded onto the reinforcing layer to obtain an unvulcanized hose-like test piece. Next, a curing tape (protective cloth) made of nylon 66 was wound around the outside of the unvulcanized hose-like test piece to perform vulcanization.

  Vulcanization was carried out under the following four conditions, and the resulting hose-like vulcanized test piece was evaluated for adhesion strength and with rubber. In addition, adhesive strength and with rubber | gum are the average values of the value measured 10 times, respectively.

(Vulcanization conditions)
-Vulcanization condition 1: An unvulcanized hose-like specimen prepared using the rubber composition immediately after kneading was vulcanized for 90 minutes in a steam can at 142 ° C (steam vulcanization).
-Vulcanization condition 2: An unvulcanized hose-like specimen prepared using the rubber composition immediately after kneading was vulcanized in an atmospheric oven at 142 ° C for 135 minutes (oven vulcanization).
-Vulcanization condition 3: After storing unvulcanized hose-like test pieces for 2 weeks in a dry environment of 25 ° C and 55% relative humidity (% RH), vulcanize for 135 minutes in a 142 ° C atmospheric pressure oven. (Oven vulcanization).
・ Vulcanization condition 4: After storing unvulcanized hose-like test pieces for 4 weeks in a dry environment of 25 ° C. and 30% relative humidity (% RH), vulcanize in an atmospheric oven at 142 ° C. for 135 minutes. (Oven vulcanization).

[With adhesive strength and rubber]
About each hose-like vulcanization test piece obtained on the above vulcanization conditions, adhesive strength (kN / m) and with rubber (%) were evaluated. Here, the adhesive strength (kN / m) is the magnitude of force per unit width (m) required for peeling the outer rubber layer from the interface between the outer rubber layer and the reinforcing layer at a peeling speed of 50 mm / min ( kN). Here, the term “with rubber” refers to the ratio of the outer rubber layer of the hose-like vulcanized test piece remaining on the surface of the reinforcing layer and the area ratio of the remaining rubber layer to the entire surface area of the reinforcing layer expressed as a percentage. is there.

  Tables 3 and 4 show the results of measurement of adhesion strength and rubber. Adhesion tests 1 to 4 in Tables 3 and 4 correspond to the test results of the test pieces prepared under the above vulcanization conditions 1 to 4. When the adhesive strength is 2.5 kN / m or more and the rubber attachment is 60% or more, it can be said that the adhesion between the outer rubber layer and the reinforcing layer is good.

Furthermore, the rubber mixing processability at the time of kneading for each composition was evaluated according to the following criteria. The evaluation results for Examples 1-9 in Table 3, Table 4 shows the evaluation results of Comparative Examples 1-9.
○: Good unity.
Δ: The unity is neither good nor bad.
X: The unity is bad.

Furthermore, the external appearance of the outer rubber layer was visually evaluated on the following criteria for each hose-like vulcanized test piece. The evaluation results for Examples 1 to 9 and Comparative Examples 8 to 9 are shown in Tables 3 and 4 , and the evaluation results for Comparative Examples 1 to 7 are shown in Table 4.
○: There is no dent-like defect (porous).
X: There is a hollow defect (porous).

As is apparent from Table 3, the compositions of Examples 1 to 9 had good rubber mixing processability, that is, the rubber compositions after kneading with a Banbury Kimizer were well organized. Also, the rubber appearance after vulcanization was good with no porosity. Furthermore, the hose-like vulcanized test pieces prepared using the compositions of Examples 1 to 9 each have an adhesive strength with the reinforcing layer of 2.5 kN / m or more, and those with rubber are 60% or more. It was. Furthermore, the hose-like vulcanized test pieces prepared using the compositions of Examples 1 to 9 had an adhesive strength of 2.5 kN / m or more after storage for 4 weeks, and 60% with rubber. That was all.

  As is clear from Table 4, for the hose-like vulcanized test pieces prepared using the compositions of Comparative Examples 1 to 7, the adhesive strength after storage for 4 weeks is less than 2.5 kN / m, All with rubber were less than 60%. In Comparative Examples 4, 5, and 7, the rubber mixing processability and the rubber appearance were poor.

1 Hydraulic hose (vulcanized rubber product)
2 inner rubber layer 3 reinforcing layer 4 outer rubber layer 6 mandrel 6C hose body 14 vulcanizer 18 nylon cloth

Claims (12)

To sulfur vulcanizable diene-based polymer 100 parts by weight,
3.0 parts by weight or more and 15 parts by weight or less of water;
0.5 to 10 parts by mass of a water absorbent resin,
A rubber layer made of a metal surface adhesive rubber composition comprising:
A rubber composition metal laminate in which a reinforcing layer having a metal surface is laminated. The rubber composition metal laminate according to claim 1, wherein the metal surface is a brass-plated metal surface. The rubber composition metal laminate according to claim 1 or 2, wherein the water-absorbent resin is at least one selected from an acrylic acid polymer partial sodium salt crosslinked product, a modified acrylic crosslinked polymer, and a polyether compound. . The rubber composition metal laminate according to claim 3, wherein the polyether compound is polyethylene oxide or polyethylene glycol. The diene polymer is selected from natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), and chloroprene rubber (CR). The rubber composition metal laminate according to any one of claims 1 to 4 , comprising at least one selected. The rubber composition metal laminate according to any one of claims 1-5 obtained by further compounding a vulcanizing agent. The rubber composition metal laminate according to any one of claims 1 to 6, wherein the metal surface is a brass-plated metal surface. The rubber composition metal laminate according to any one of claims 1 to 7, wherein the reinforcing layer has a braided (blade) structure in which wires are knitted or a spiral structure. A vulcanized rubber product in which the rubber layer of the rubber composition metal laminate according to any one of claims 1 to 8 is vulcanized in the presence of a sulfur-containing vulcanizing agent and bonded to the reinforcing layer. The vulcanized rubber product according to claim 9 , which is a hydraulic hose or a high-pressure hose. The vulcanized rubber product according to claim 10 , wherein the hydraulic hose or the high-pressure hose is vulcanized by passing through an oven vulcanizer. A laminating step of laminating a reinforcing layer having a surface plated with brass and at least one rubber layer to produce a laminate;
Passing through the laminate in an oven vulcanizer, vulcanizing the rubber layer, and bonding to the brass plated reinforcing layer,
The rubber layer is
For 100 parts by mass of the sulfur vulcanizable diene polymer,
3 . 0 parts by weight or more and 15 parts by weight or less of water;
0.5 to 10 parts by mass of a water absorbent resin,
A rubber composition comprising:
A method for producing a vulcanized rubber product, further comprising a sulfur-containing vulcanizing agent.

Images