TWI662083B - Rubber composition, rubber composition metal laminate, and vulcanized rubber product - Google Patents

Abstract

The present invention provides a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product which can obtain a rubber layer having excellent adhesion to a metal surface. The rubber composition of the present invention is characterized in that it contains 0.5 to 4 parts by mass of sulfur, and 0.004 to 0.17 mol, based on 100 parts by mass of a diene polymer capable of being vulcanized with sulfur. Polyol compounds having a molecular weight of 300 or less below.

Description

Rubber composition, rubber composition metal laminate, and vulcanized rubber product

The present invention relates to a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product. Specifically, the present invention relates to a rubber composition containing a vulcanizing agent, a rubber composition metal laminate, and a vulcanized rubber product.

In the past, a pair of rubber layers has been proposed to consist of a pair of rubber layers that clamp the surface of a reinforced layer coated with a metal such as brass (Brass) and a chloroprene-based rubber for the manufacture of high-pressure hoses. (For example, refer to Patent Document 1). The rubber composition contains sulfur-based and guanidine-based vulcanization accelerators, so the crosslinking characteristics of the rubber layer composed of the rubber composition can be improved, and the adhesion between the metal surface of the reinforcing layer and the rubber layer is good. .

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-279022

The method for manufacturing the hose includes a steam vulcanization method in which the rubber composition is heated by steam to vulcanize the rubber composition, and an oven vulcanization method in which the rubber composition is vulcanized in an oven to vulcanize the rubber composition. The oven vulcanization method can continuously perform vulcanization, thereby improving the productivity of the hose.

However, when the rubber composition is vulcanized by an oven vulcanization method, the evaporation of moisture during vulcanization is significant, and it may not necessarily be possible to obtain sufficient adhesion between the rubber layer and the reinforcing layer. Therefore, not only the steam vulcanization method, but also the vulcanization method by a hot air vulcanization method such as an oven vulcanization method, a rubber composition capable of obtaining a rubber layer having excellent adhesion to the metal surface of the reinforcing layer is desired.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product which can obtain a rubber layer having excellent adhesion to a metal surface.

The rubber composition of the present invention is characterized in that it contains 0.5 to 4 parts by mass of sulfur, and 0.004 to 0.17 mol, based on 100 parts by mass of a diene polymer capable of being vulcanized with sulfur. Polyol compounds having a molecular weight of 300 or less below.

According to this rubber composition, since the content of sulfur in the rubber composition and the hydroxyl equivalent derived from the polyol compound are in a moderate range, Therefore, the catalyst function of the bond formation reaction between the sulfur and the metal surface brought by the polyol compound can be effectively exhibited. This allows the rubber composition to be vulcanized by any of the hot air vulcanization method and steam vulcanization method in which the composition is easy to dry, so that a rubber layer having excellent adhesion to metal surfaces such as a reinforcing layer can be obtained.

In the rubber composition of the present invention, the polyol compound is preferably a compound represented by the following general formula (1).

(In formula (1), R ₁ represents a hydrogen atom or a mono- or polyhydroxyalkyl group having 1 or more and 5 or less carbon atoms that can contain an ether bond and a branch, and R ₂ represents 1 or more carbon atoms that can contain an ether bond and a branch and 5 or less mono or polyhydroxyalkyl)

The rubber composition metal laminate of the present invention includes a reinforcing layer having a metal surface and a rubber layer containing the rubber composition provided on the metal surface.

According to the rubber composition metal laminate, since the content of sulfur in the rubber composition and the hydroxyl equivalent derived from the polyol compound are in a moderate range, the sulfur caused by the polyol compound and the surface of the metal can be efficiently exhibited. The catalytic function of the bond formation reaction. As a result, the rubber composition metal laminate, whether it is hot air sulfur which is easy to dry using the composition Both the curing method and the steam curing method can be vulcanized to obtain a rubber composition metal laminate having excellent adhesion between the metal surface of the reinforcing layer and the rubber layer.

In the rubber composition metal laminate of the present invention, the metal surface is preferably formed by brass plating.

In the rubber composition metal laminate of the present invention, the reinforcing layer preferably has a braid structure or a spiral structure obtained by weaving a wire.

The vulcanized rubber product of the present invention is obtained by using the rubber composition described above.

The vulcanized rubber product of the present invention is preferably a vulcanized rubber product that vulcanizes the rubber layer of the metal composition of the rubber composition in the presence of sulfur and adheres to the reinforcing layer.

In the vulcanized rubber product of the present invention, a hose is preferred.

According to the present invention, it is possible to realize a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product which can obtain a rubber layer having excellent adhesion to a metal surface.

1‧‧‧Hydraulic hose

11‧‧‧Inner rubber layer

12‧‧‧ reinforcement layer

13‧‧‧outer rubber layer

100‧‧‧ Unwinder

101‧‧‧ mandrel

102‧‧‧The first extruder

103‧‧‧Hose

104‧‧‧ Take-up and unwinding machine

105‧‧‧knitting machine

106‧‧‧hose

107‧‧‧ Take-up and unwinding machine

108‧‧‧Second Extruder

109‧‧‧Hose body

110‧‧‧ Winder

111‧‧‧Vulcanization unit

112‧‧‧hose

113‧‧‧ coating device

114‧‧‧Unwrapping device

115‧‧‧hose

116‧‧‧Hose

117‧‧‧Spindle extraction device

118‧‧‧hose

119‧‧‧ nylon cloth

120‧‧‧ hot air

FIG. 1 is a schematic partially cutaway perspective view showing an example of a hydraulic hose according to an embodiment of the present invention.

Fig. 2 is an explanatory diagram of a manufacturing process of a hydraulic hose using the rubber composition according to the embodiment of the present invention.

FIG. 3 is an explanatory diagram of a vulcanization step of an oil pressure hose using the rubber composition according to the embodiment of the present invention.

FIG. 4 is a partial cross-sectional view showing an example of a layer structure put around a mandrel of a vulcanizing device in a manufacturing step of a hydraulic hose using the rubber composition according to the embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the attached drawings. The present invention is not limited to the following embodiments, and can be appropriately modified and implemented.

The rubber composition according to this embodiment contains, based on 100 parts by mass of a diene polymer that can be vulcanized with sulfur, 0.5 to 4 parts by mass of sulfur, and a molecular weight of 0.004 to 0.17 mol. Polyol compounds below 300.

According to this rubber composition, since the diene polymer contains a predetermined amount of sulfur and a predetermined amount of a polyol compound, the sulfur content and the hydroxyl equivalent in the rubber composition are in a moderate range, and may be Efficiently exhibits the catalyst function of the reaction of sulfur and metal surface bond formation brought about by the polyol compound. With this, the rubber composition is vulcanized by any of the hot air vulcanization method using steam which is easy to dry and reduces the catalyst function of the bond formation reaction between sulfur and the metal surface, and steam vulcanization method. , Can get metal surface and rubber layer A rubber layer with excellent adhesion. Hereinafter, various components of the rubber composition of this embodiment will be described in detail.

<Diene polymer>

Diene polymers are those which can be vulcanized with sulfur. Here, the term "sulfurizable with sulfur" means that it has the property of forming a crosslinked structure using sulfur as a medium. Examples of other diene polymers include natural rubber (NR), chloroprene rubber (CR), isoprene rubber (IR), styrene butadiene rubber (SBR), and acrylonitrile-butadiene. Ethylene rubber (NBR), ethylene-propylene-diene rubber (EPDM), chlorinated polyethylene rubber (CM), and chlorinated polyethylene rubber (CSM). By using these, the various physical properties for a hose required for a rubber composition can be exhibited to a high degree. Among these, from the viewpoint of high adhesion between the metal surface and the rubber layer from which the reinforcing layer can be obtained, chloroprene rubber (CR), styrene butadiene rubber (SBR), and acrylonitrile- Butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM). These diene polymers may be used alone or in combination of two or more.

The blending amount of the diene polymer is preferably 20% by mass or more and 70% by mass or less based on the entire rubber composition from the viewpoint of good rubber mixing processability and the viewpoint of good rubber appearance.

<Vulcanizing agent>

The rubber composition of this embodiment contains sulfur as a vulcanizing agent. Examples of the sulfur include powder sulfur, sedimentary sulfur, highly dispersible sulfur, surface-treated sulfur, and insoluble sulfur.

The content of sulfur is 0.5 parts by mass or more and 4.0 parts by mass or less based on 100 parts by mass of the diene polymer. When the sulfur content is 0.5 parts by mass or more and 4.0 parts by mass or less, when the rubber composition is vulcanized, the bond between sulfur and the metal surface can be sufficiently formed, and sufficient adhesion between the rubber layer and the metal surface can be obtained. From the viewpoint of the adhesion between the rubber layer and the metal surface, the sulfur content is preferably 0.55 parts by mass or more, more preferably 0.6 parts by mass or more, and more preferably 100 parts by mass of the diene polymer. 0.65 parts by mass or more, more preferably 0.7 parts by mass or more, more preferably 3.75 parts by mass or less, particularly preferably 3.5 parts by mass or less, more preferably 3.25 parts by mass or less, and even more preferably 3.0 parts by mass or less. Taking the above into consideration, the sulfur content is preferably 0.55 parts by mass or more and 3.75 parts by mass or less, more preferably 0.6 parts by mass or more and 3.5 parts by mass or less, based on 100 parts by mass of the diene polymer. It is 0.65 parts by mass or more and 3.25 parts by mass or less, and more preferably 0.7 parts by mass or more and 3.0 parts by mass or less.

The rubber composition of this embodiment may contain a vulcanizing agent other than sulfur as long as the effect of the present invention can be achieved. Examples of the vulcanizing agent other than sulfur include sulfur-based, organic peroxide-based, metal oxide-based, phenol resin, and benzoquinone dioxime. These can be used individually by 1 type or in combination of 2 or more types. Examples of the sulfur-based vulcanizing agent include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), and disulfide tetrasulfide. Organic sulfur-containing compounds such as amyl thiuram (DPTT), tetrabenzyl thiuram disulfide, dimorpholine disulfide, and alkylphenol disulfide.

Examples of the organic peroxide-based vulcanizing agent include dicumyl peroxide, benzamidine peroxide, tert-butyl hydrogen peroxide, 2,4-dichlorobenzyl peroxide, and 2,5-di Methyl-2,5-di (tertiary-butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (benzoate peroxy).

Examples of other vulcanizing agents include resins such as zinc oxide, magnesium oxide, and phenol resins, p-benzoquinonedioxime, p-benzophenazinebenzoquinonedioxime, poly-p-dinitrosobenzene, and methylenediphenylamine. Wait.

<Vulcanization accelerator>

The rubber composition of this embodiment preferably further contains a vulcanization accelerator. Examples of the vulcanization accelerator include aldehyde-ammonia-based vulcanization accelerators, aldehyde-amine-based vulcanization accelerators, thiourea-based vulcanization accelerators, guanidine-based vulcanization accelerators, thiazole-based vulcanization accelerators, and sulfenamide-based vulcanization accelerators. Agent, thiuram-based vulcanization accelerator, dithiaminate-based vulcanization accelerator, and xanthate-based vulcanization accelerator. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram monosulfide (TS) and tetramethylthiuram disulfide (TT). Examples of the guanidine-based vulcanization accelerator include diphenylguanidine. Examples of the sulfenimide-based vulcanization accelerator include N-tertiary-butylbenzothiazole-2-sulfenimide and the like. Examples of the thiourea-based vulcanization accelerator include ethylene thiourea and the like.

The content of the vulcanization accelerator is preferably 0.5 parts by mass or more from the viewpoint of improving the vulcanization characteristics to improve the adhesion between the rubber layer using the rubber composition and the metal surface, relative to 100 parts by mass of the diene polymer. , Particularly preferably 0.75 parts by mass or more, more preferably 1.0 part by mass or more, In addition, it is preferably 3.5 parts by mass or less, particularly preferably 3.0 parts by mass or less, and even more preferably 2.5 parts by mass or less.

<Polyol>

The rubber composition of this embodiment contains a polyol compound having a molecular weight of 300 or less. As the polyol compound, as long as it is a compound having a molecular weight of 300 or less and containing two or more hydroxyl groups, as long as the effects of the present invention can be achieved, various compounds can be used. This polyhydric alcohol compound has a catalyst function for forming a bond between sulfur and a metal atom on a metal surface when the rubber composition is vulcanized, so that the rubber layer containing the rubber composition and the metal surface can be improved. Adhesiveness.

In the rubber composition of the present embodiment, the polyol compound is preferably a polyol compound represented by the following general formula (1) from the viewpoint of adhesion between the rubber layer and the reinforcing layer of the rubber composition.

(In formula (1), R ₁ represents a hydrogen atom or a mono- or polyhydroxyalkyl group having 1 or more and 5 or less carbon atoms that can contain an ether bond and a branch, and R ₂ represents 1 or more carbon atoms that can contain an ether bond and a branch and 5 or less mono or polyhydroxyalkyl)

Examples of R ₁ in the general formula (1) include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, dihydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, and 3-hydroxy. Propyl, dihydroxypropyl, trihydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, dihydroxybutyl, trihydroxybutyl, tetrahydroxybutyl Base, pentahydroxybutyl, 1-hydroxypentyl, 2-hydroxypentyl, 3-hydroxypentyl, 4-hydroxypentyl, 5-hydroxypentyl, dihydroxypentyl, trihydroxypentyl, tetrahydroxypentyl Methyl, pentahydroxypentyl, methoxymethyl, hydroxyethoxyethyl, dihydroxypropoxymethyl, dihydroxypropoxyethyl, trihydroxypropoxymethyl, and trihydroxypropoxy Ethyl etc.

Examples of R ₂ in the general formula (1) include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, dihydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, and 3-hydroxy. Propyl, dihydroxypropyl, trihydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, dihydroxybutyl, trihydroxybutyl, tetrahydroxybutyl Base, pentahydroxybutyl, 1-hydroxypentyl, 2-hydroxypentyl, 3-hydroxypentyl, 4-hydroxypentyl, 5-hydroxypentyl, dihydroxypentyl, trihydroxypentyl, tetrahydroxypentyl Methyl, pentahydroxypentyl, methoxymethyl, hydroxyethoxyethyl, dihydroxypropoxymethyl, dihydroxypropoxyethyl, trihydroxypropoxymethyl, and trihydroxypropoxy Ethyl etc.

Examples of the polyhydric alcohol compound represented by the general formula (1) include ethylene glycol, propylene glycol, butanediol, pentanediol, diethylene glycol, triethylene glycol, glycerol, and Hydroxyhexane, diglycerin, trimethylolpropane, neopentaerythritol, sorbitol, hexanetriol, etc. Among these, a rubber having excellent adhesion between a rubber layer and a metal surface using a rubber composition is obtained. From the viewpoint of the composition, it is preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, glycerol, hexanetriol, diglycerol, and sorbitol.

The content of the polyol compound is 0.004 mol or more and 0.17 mol or less based on 100 parts by mass of the diene polymer. If the content of the polyhydric alcohol compound is within the above range, the hydroxyl equivalent in the rubber composition is in a moderate range, so the catalyst effect of the bond reaction between sulfur and the metal surface can be sufficiently obtained, and the rubber composition can be obtained. A composition having excellent adhesion between a rubber layer and a metal surface. The content of the polyhydric alcohol compound is preferably 0.01 mol or more, more preferably 0.02 mol or more, and more preferably 0.165 mol or less, and more preferably 0.0155 mol or less with respect to 100 parts by mass of the diene polymer. As described above, the content of the polyol compound is preferably 0.01 mol or more and 0.165 mol or less, and particularly preferably 0.02 mol or more and 0.155 mol or less with respect to 100 parts by mass of the diene polymer.

[Other additives]

In addition, the rubber composition may contain other additives as necessary as long as the effects of the present invention can be achieved. Other additives include, for example, fillers, plasticizers, softeners, anti-aging agents, organic active agents, antioxidants, anti-charge agents, flame retardants, cross-linking promoters, vulcanization retarders, ozone degradants, Processing oil (aromatic oil) and adhesion aid.

Examples of the filler include carbon black, silicon dioxide (white carbon), clay, talc, iron oxide, zinc oxide (ZnO), titanium oxide, and oxide. Barium, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium sulfate, mica, and diatomaceous earth. These can be used individually by 1 type or in combination of 2 or more types. Carbon black can be appropriately selected and used according to the application. The carbon black is preferably an ISAF grade, a FEF grade, or the like. Examples of the silicon dioxide include crystalline silicon dioxide, precipitated silicon dioxide, amorphous silicon dioxide (for example, high-temperature-treated silicon dioxide), smoked silicon dioxide, sintered silicon dioxide, precipitated silicon dioxide, and pulverization. Silicon dioxide, and fused silica. In particular, since silicon dioxide is the same as carbon black, it is known that carbon gel (bonded rubber) is formed, and therefore it can be preferably used as necessary. Examples of the clay include hard clay, paraffin clay, kaolin clay, and sintered clay.

Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), isodecyl succinate, and diethyl dibenzoate. Glycol esters, neopentyl glycol esters, butyl oleate, methyl ricinoleate, tricresol phosphate, trioctyl phosphate, trimellitate, propylene glycol adipate, and adipic acid Butanediol polyester, naphthenic oil, etc. These can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the softening agent include aromatic oils, naphthenic oils, paraffin oils, petroleum resins, vegetable oils, and liquid rubbers. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the anti-aging agent include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD) and N, N'-dinaphthyl-p-phenylenediamine (DNPD) , N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), styrenated phenol (SP), and 2,2,4-trimethyl-1,2-dihydroquinoline polymer ( RD) and so on. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the organic active agent include stearic acid, oleic acid, lauric acid, and zinc stearate. These can be used individually by 1 type or in combination of 2 or more types.

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

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

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

Crosslinking promoters can be used together with general rubber promoters. Examples of rubber auxiliary agents include zinc oxide, stearic acid, oleic acid, and Zn salts thereof.

Examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid, salicylic acid, and salicylic acid; N-nitroso-diphenylamine, N-nitroso-phenyl-β -Nitroso compounds such as naphthylamine, N-nitroso-trimethyl-dihydroquinoline polymers; halides such as trichloromelan; 2-mercaptobenzimidazole, and N- (cyclohexyl Thio) phthalimide (PVI) and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the adhesion promoter include triazine thiol compounds (for example, 2,4,6-trimercapto-1,3,5-triazine, 6-butylamino-2,4-dimercapto-1, 3,5-triazine), resorcinol, cresol, resorcinol-formalin latex, Monomethylolmelamine, monomethylolurea, vinylmaleimide, cobalt naphthenate, cobalt stearate, cobalt tert-carbonate, and cobalt dodecanoate. These can be used individually by 1 type or in combination of 2 or more types.

<Manufacturing method of rubber composition>

The rubber composition of this embodiment can be produced by a conventionally known production method. In the method for producing a rubber composition according to this embodiment, for example, first, the above-mentioned diene-based polymer, as well as other diene-based polymers and polymers other than the diene-based polymer, and various additives described above are prepared as necessary. Then use the Banbury mixer, kneader and other closed mixers; rollers and other kneading rollers, extruders, and biaxial extruders, etc. to carry out the kneading manufacturing method.

[Rubber composition metal laminate]

The rubber composition metal laminate of this embodiment is a laminate of the rubber composition and a wire reinforcing layer formed by metal plating on the surface. Examples of the laminate include a high-pressure hose and a hydraulic hose. Fig. 1 is a partially cutaway perspective view showing an example of a hydraulic hose according to this embodiment. As shown in FIG. 1, the hose 1 includes an inner rubber layer 11 formed in a cylindrical shape and a fluid passing through the interior, a reinforcing layer 12 provided outside the inner rubber layer 11, and an outer rubber layer 12 provided outside the reinforcing layer 12.外 胶层 13。 The outer rubber layer 13. The reinforcing layer 12 is disposed so as to be sandwiched between the inner rubber layer 11 and the outer rubber layer 13. The inner rubber layer 11, the reinforcing layer 12, and the outer rubber layer 13 are adhered by vulcanization of the inner rubber layer 11 and the outer rubber layer 13. fixed.

<Rubber layer>

As described above, the inner rubber layer 11 and / or the outer rubber layer 13 are rubber layers using the rubber composition of the above embodiment. From the viewpoint of the weather resistance of the hose, it is preferable to form at least the outer rubber layer 13 using the rubber composition of the above embodiment. The inner rubber layer 11 is preferably formed using a rubber composition containing acrylonitrile butadiene rubber (NBR) having excellent oil resistance as a main component.

The thickness of the internal rubber layer 11 is preferably, for example, 0.2 mm or more and 4.0 mm or less, and particularly preferably 0.5 mm or more and 2.0 mm or less. Similarly, the thickness of the outer rubber layer 13 is preferably 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.

<Reinforcement layer>

The reinforcing layer 12 is made of braided wire made of steel wire, and the surface of the wire is made of brass. From the viewpoint of maintaining the strength of the hydraulic hose 1, it is a layer provided between the inner rubber layer 11 and the outer rubber layer 13. In the example shown in FIG. 1, the reinforcing layer 12 is configured as a single layer, but a plurality of reinforcing layers 12 having an intermediate rubber layer disposed between the layers may be provided. The reinforcing layer 12 may be formed by winding a steel wire wire into a spiral-shaped spiral wire around the inner rubber layer 11 in addition to the wire weaving. The materials and knitting or weaving or winding methods for forming the reinforcing layer 12 can be adapted to the application. For example, it is appropriately selected in accordance with the pressure resistance. In the hydraulic hose and the like, the reinforcing layer 12 is preferably formed by weaving a wire.

Examples of the wire material include piano wires (carbon steel), hard steel wires, and stainless steel wires. From the viewpoints of workability and strength, the wire materials are particularly preferably piano wires (carbon steel) and hard steel wires.

In order to improve the adhesion with the rubber layer, the reinforcing layer 12 is formed by metal plating. The metal plating layer is formed by applying brass (Brass) to piano wires and hard steel wires. In brass coating, copper is plated on steel wire, and zinc is plated on copper, and a thermal diffusion treatment is applied to form a brass coating.

<Vulcanized rubber products>

The rubber composition and the rubber composition metal laminate of the reinforcing layer 12 are crosslinked in the presence of sulfur, that is, vulcanized, and the molecules of the rubber forming the inner rubber layer 11 and the outer rubber layer 13 are formed by the sulfur. Cross-linking. By this crosslinking, elasticity and tensile strength can be imparted to the inner rubber layer 11 and the outer rubber layer 13, and a brass-coated metal (copper, zinc) and sulfur bonds can be formed on the interface with the reinforcing layer 12. The inner rubber layer 11 and the outer rubber layer 13 and the reinforcing layer 12 are adhered and bonded.

Sulfur is preferably formulated with other materials in advance when a compound is formed as a rubber composition. Sulfur can be blended as long as the molecular chains forming the diene polymer can be cross-linked with each other through sulfur, and at the interface between the inner rubber layer 11 and the outer rubber layer 13 and the reinforcing layer 12, metal (copper, zinc) is used. In the case where the inner rubber layer 11 and the outer rubber layer 13 and the reinforcing layer 12 are adhered to each other by bonding with sulfur, the compounding of the compound is not limited.

Examples of the vulcanization method include a method in which a rubber composition is heat-treated at a predetermined temperature for a predetermined time in the presence of sulfur. The curing temperature is preferably 130 ° C or higher and 180 ° C or lower. The curing time is preferably 30 minutes or more and 240 minutes or less. By combining the temperature and time in this range, desired physical properties such as elasticity, tensile strength, appearance, rubber-metal interface adhesion and rubber-metal interface rubber adhesion can be obtained as vulcanized rubber products.

The vulcanized rubber product of this embodiment can be preferably used as a hydraulic hose or the like. Examples of the method for manufacturing hydraulic hoses include a vapor vulcanization method in which a rubber composition metal laminate is enclosed in a high-pressure container and crosslinked in a steam tank, and a rubber composition is covered with a nylon cloth or the like. An oven vulcanization method in which a metal laminate is vulcanized in a hot-air drying furnace. Generally speaking, the steam curing method is batch processing, and the oven curing method is continuous processing. The manufacturing method of the hydraulic hose is preferably an oven curing method of continuous processing.

<Manufacturing method of vulcanized rubber products>

The following is a description of a method for manufacturing a vulcanized rubber product according to this embodiment. Here, the case of manufacturing a hydraulic hose as a vulcanized rubber product will be described as an example.

The manufacturing method of the hydraulic hose according to this embodiment will be described with reference to FIGS. 2 and 3. FIG. 2 is an explanatory diagram of the manufacturing steps of the hydraulic hose using the rubber composition of the embodiment of the present invention, and FIG. 3 is the vulcanizing steps of the hydraulic hose using the rubber composition of the embodiment of the present invention. Illustrating.

<Hose Manufacturing Procedure>

As shown in FIG. 2, the rubber hose is obtained by the following steps: a pressing step of the rubber material forming the inner rubber layer 11 (step S101), a weaving step of the reinforcing layer 12 (step S102), and an outer rubber layer 13 Step of extrusion / vulcanization (step S103), and step of extracting the mandrel 101 (step S104). The manufactured rubber hoses are inspected by water pressure, and then the winding process is checked.

First, in step S101, an unvulcanized inner rubber layer 11 is coated on the outer peripheral surface of a mandrel 101 drawn out from a winder 100 by a first extruder 102. The hose 103 covered with the inner rubber layer 11 is taken up by a take-up and unwinding machine 104.

Next, in step S102, in order to cover the inner rubber layer 11 constituting the hose 103 pulled out from the winding and unwinding machine 104, the hose 106, which is to be reinforced by the knitting machine 105 to form the reinforcing layer 12, is wound. Taken in the take-up reel 107. The wires of the reinforcing layer 12 are made of metal wires. In order to achieve good adhesion to rubber, metal wires are made of brass-plated steel wires. The reinforcing layer 12 may be formed by spirally winding a metal wire around the inner rubber layer 11 formed around the mandrel 101.

Next, in step S103, the unvulcanized outer rubber layer 13 is coated on the reinforcing layer 12 of the hose 106 pulled out from the winding and unwinding machine 107 by the second extruder 108 to form a hose body 109. And all The formed hose body 109 is taken up by a winder 110. In the present embodiment, after the hose body 109 is pulled out from the second extruder 108 and is wound up between the coiler 110, the coiler 110 is wound up by the vulcanizing device 111 and vulcanized by the vulcanization step 111 to vulcanize The hose 112, but the vulcanization step may be provided after the hose body 109 is wound by the coiler 110. In addition, before and after the vulcanizing device 111, a covering device 113 and an uncoating device 114 for attaching and detaching a protective cloth such as a nylon cloth to the hose body 109 are provided. In FIG. 2, the hose 115 before the vulcanization of the nylon cloth is taken up by the covering device 113, and after the vulcanization, the hose 116 before the vulcanization of the nylon cloth is removed. The vulcanization step will be detailed later.

Next, in step S104, after the vulcanization, the mandrel 101 is pulled out from the mandrel 110 unwound by the coiler 110 and unwrapped, thereby completing the hose 118.

<Vulcanization step>

As shown in FIG. 3, the hose body 109 pulled out from the second extruder 108 is wound around the nylon cloth 119 by the covering device 113. The hose body 109 covered with the nylon cloth 119 is carried into the vulcanizing device 111. The vulcanizing device 111 is a continuous vulcanizing device of a hot-air circulation type that performs vulcanization by hot air 120. This curing method is an oven curing method.

FIG. 4 is a partial cross-sectional view showing an example of a layer structure put around a mandrel 101 of a vulcanizing device. As shown in FIG. 4, an inner rubber layer 11 is formed around the mandrel 101, a reinforcing layer 12 is formed around the periphery, and an outer rubber layer 13 is further formed around the periphery. On outer rubber A nylon cloth 119 is wound around the layer 13 and is heated in this state to perform a vulcanization step.

As described above, the curing temperature is preferably 130 ° C. or higher and 180 ° C. or lower, and the curing time, that is, the curing time in the curing device 111 is preferably 30 minutes or more and 240 minutes or less. Under this temperature range and vulcanization time, a hydraulic hose with good adhesion between the inner rubber layer 11 and the outer rubber layer 13 and the reinforcing layer 12 can be obtained. Here, by using the rubber composition of the above embodiment to form the inner rubber layer 11 and / or the outer rubber layer 13, the adhesion between the inner rubber layer 11 and / or the outer rubber layer 13 and the metal reinforcing layer 12 can be manufactured. Good hydraulic hose.

According to the rubber composition, moderate moisture can be stably held in the composition until just before vulcanization. Therefore, even in an oven vulcanization method in which moisture evaporates, it is possible to suppress poor adhesion and adhesion caused by insufficient moisture. The reduction. However, of course, the rubber composition of the above embodiment can also be preferably used for the production of rubber products of other vulcanization methods known in the past. Other curing methods include, for example, compression curing, steam curing, and warm water curing.

In addition, in the above embodiment, the manufacturing steps according to the continuous processing method are exemplified, but a vulcanized rubber product can also be manufactured by a method of manufacturing a rubber layer and a reinforcing layer in different steps and then bonding them.

The hydraulic hose manufactured by the manufacturing method of this embodiment can be applied to various applications. The use of the hydraulic hose can be preferably used, for example, as an automotive air conditioning hose, a power steering hose, a hydraulic hose used in a hydraulic system for building a vehicle, and the like.

In the present embodiment, a hydraulic hose is used as the rubber composition metal laminate and the vulcanized rubber product. However, the present invention is not limited to this. For example, other rubber laminates such as conveyor belts can be used in the same manner .

As described above, according to the manufacturing method of the rubber composition metal laminate, the vulcanized rubber product, and the vulcanized rubber product, a vulcanized rubber product having good adhesion between the rubber layer and the reinforcing layer can be provided even in the continuous production method of the oven vulcanization method. In particular, even when the vulcanized rubber product is used after long-term storage in a hot and humid state, it can provide a composition of a rubber product with good adhesion to the reinforcing layer. This vulcanized rubber product can be preferably used in hydraulic hoses, high-pressure hoses, and the like.

Examples

Hereinafter, the present invention will be described in more detail with reference to examples performed to clarify the effects of the present invention. The present invention is not limited to the following examples and comparative examples.

<1. Preparation of rubber composition> (Example 1)

Contains: Acrylonitrile-butadiene rubber (trade name "Nancar 3345", manufactured by Nandi Chemical Industry Co., Ltd., acrylonitrile content 34% by mass, Mooney Viscosity (ML1 + 4, 100 ° C) 45) 40% by mass, ethylene-propylene-diene rubber (trade name "EPT 4070", manufactured by Mitsui Chemicals, 56% by mass of ethylene, and 8% of ethylidene norbornene % By mass, Mooney viscosity (ML1 + 4, 125 ° C) 47) 30% by mass, and styrene butadiene rubber (trade name "Nipol 1502", manufactured by Zeon Japan, emulsion polymerization SBR, bonded styrene content 23.5 In terms of mass%, Mooney viscosity (ML1 + 4, 100 ° C) 52) 30 mass% of 100 parts by mass of the diene polymer, blending: 2.3 mass parts of sulfur (manufactured by Hokai Chemical Industry Co., Ltd.) and 0.05 mol of Ethylene glycol (manufactured by Japan Catalyst Corporation), and 1.7 parts by mass of a sulfenamide-based vulcanization accelerator (N-tertiary-butylbenzothiazole-2-sulfenamide, trade name "Nocceler NS-P" , Manufactured by Onai Shinko Chemical Industry Co., Ltd.), with 0.3 parts by mass of an anti-coking agent (N-cyclohexylthiophthalimide, manufactured by FLEXSYS), and 62 parts by mass of ISAF-grade carbon black (trade name " Show Black N220 '', manufactured by Showa Cabot), 15 parts by mass of hard clay (trade name "Suprex Clay", manufactured by Kentucky Tennessy Clay Company), and 5 parts by mass of zinc oxide, 3rd type (Jingtong Chemical Industry Co., Ltd.) (Manufactured), 1 part by mass of stearic acid (manufactured by Nippon Oil & Fats Co., Ltd.), and 2.4 parts by mass of anti-ozone degradant (trade name "Ozono" "ne 6C", manufactured by Seiko Chemical Co., Ltd., and 10 parts by mass of a plasticizer (dioctyl adipate, trade name "DIACIZER DOA", manufactured by Mitsubishi Kasei Vinyl Corporation), and 12 parts by mass of processing oil (aromatic oil, commercial product) Named "A-OMIX", manufactured by Sankyo Petrochemical Industry Co., Ltd.), and kneaded with a Banbury mixer to produce a rubber composition. The adhesiveness of the produced rubber composition was evaluated. The blending amount of each component is shown in Table 1 below.

(Example 2)

A rubber composition was produced and evaluated in the same manner as in Example 1 except that the blending amount of ethylene glycol was 0.16 mol. The blending amount of each component is shown in Table 1 below.

(Example 3)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.03 mol of diethylene glycol was blended instead of ethylene glycol. The blending amount of each component is shown in Table 1 below.

(Example 4)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.0043 mol of glycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd.) was prepared in place of ethylene glycol. The blending amount of each component is shown in Table 1 below.

(Example 5)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blended amount of glycerin was 0.043 mol. The blending amount of each component is shown in Table 1 below.

(Example 6)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blended amount of glycerin was 0.155 mol. The blending amount of each component is shown in Table 1 below.

(Example 7)

Except that 0.15 mol of 1,2,6-hexanetriol (manufactured by Tokyo Chemical Industry Co., Ltd.) was blended in place of ethylene glycol, a rubber composition was prepared and evaluated in the same manner as Example 1. The blending amount of each component is shown in Table 1 below.

(Example 8)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.04 mol of diglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) was prepared in place of ethylene glycol. The blending amount of each component is shown in Table 1 below.

(Example 9)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.03 mol of sorbitol (manufactured by Kao Corporation) was blended in place of ethylene glycol. The blending amount of each component is shown in Table 1 below.

(Example 10)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blending amount of sulfur was 4 parts by mass. The blending amount of each component is shown in Table 1 below.

(Example 11)

Contains: styrene butadiene rubber (trade name "Nipol 1502", manufactured by Zeon Japan, emulsion polymerization SBR, bonded styrene Content 23.5 mass%, Mooney viscosity (ML1 + 4, 100 ° C) 52) 40 mass% and chloroprene rubber (trade name "Denka Chloroprene S-41", manufactured by Denki Chemical Industries, Inc., non-sulfur modified chloroprene Diene rubber, Mooney viscosity (ML1 + 4, 125 ° C) 47) 60 parts by mass of 100 parts by mass of a diene polymer, formulated with 0.043 mol of glycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd.) Sulfur (manufactured by Hokai Chemical Industry Co., Ltd.), 0.8 mass parts of thiuram vulcanization accelerator (tetramethyl thiuram monosulfide, trade name "Sanceler TS-G", manufactured by San Shin Chemical Co., Ltd.), and 0.8 Parts by mass of guanidine-based vulcanization accelerator (diphenylguanidine, trade name "Soxinol DG", manufactured by Sumitomo Chemical Co., Ltd.), and 95 parts by mass of FEF-grade carbon black (trade name "HTC # 100", manufactured by NSCC Carbon) With 3 parts by mass of zinc oxide (manufactured by Zhengtong Chemical Industry Co., Ltd.), 3 parts by mass of magnesium oxide (trade name "Kyowamag 150", manufactured by Kyowa Chemical Industry Co., Ltd.), and 2 parts by mass of stearic acid (Manufactured by Nippon Oil & Fats Co., Ltd.), and 2.0 parts by mass of an anti-ozone degradant (trade name "Ozonone 6C"), Seiko Chemical Corporation Ltd.), 22 parts by mass, and process oil (aromatic oil, trade name "A-OMIX", Sankyo OIL CHEMICAL Co., Ltd.), and kneaded by a Banbury mixer to prepare a rubber composition. The adhesiveness of the produced rubber composition was evaluated. The blending amount of each component is shown in Table 1 below.

(Comparative example 1)

Except that no ethylene glycol was prepared, a rubber composition was prepared and evaluated in the same manner as in Example 1. The blending amount of each component is shown in Table 2 below.

(Comparative example 2)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blended amount of glycerin was 0.003 mol. The blending amount of each component is shown in Table 2 below.

(Comparative example 3)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blended amount of glycerin was 0.174 mol. The blending amount of each component is shown in Table 2 below.

(Comparative Example 4)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that the blending amount of ethylene glycol was 0.18 mol. The blending amount of each component is shown in Table 2 below.

(Comparative example 5)

A rubber composition was prepared and evaluated in the same manner as in Example 4 except that the blended amount of glycerin was 0.10 mol and the blended amount of sulfur was 4.5 parts by mass. The blending amount of each component is shown in Table 2 below.

(Comparative Example 6)

A rubber was prepared in the same manner as in Example 4 except that the blending amount of glycerin was 0.10 mol and the blending amount of sulfur was 0.45 parts by mass. Composition and evaluation. The blending amount of each component is shown in Table 2 below.

(Comparative Example 7)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.02 mol of polyglycerol A (molecular weight 330) was blended in place of ethylene glycol. The blending amount of each component is shown in Table 2 below.

(Comparative Example 8)

A rubber composition was prepared and evaluated in the same manner as in Example 1 except that 0.02 mol of polyglycerol B (molecular weight 500) was blended instead of ethylene glycol. The blending amount of each component is shown in Table 2 below.

(Comparative Example 9)

A rubber composition was prepared and evaluated in the same manner as in Example 11 except that the blending amount of glycerin was 0.003 mol and the blending amount of sulfur was 0.8 parts by mass. The blending amount of each component is shown in Table 2 below.

(Comparative Example 10)

A rubber composition was prepared and evaluated in the same manner as in Comparative Example 9 except that the blending amount of glycerin was 0.174 mol. The blending amount of each component is shown in Table 2 below.

The details of each component described in Tables 1 and 2 are as follows.

‧NBR: Trade name "Nancar 3345", manufactured by Nandi Chemical Industry Company, acrylonitrile content 34% by mass, Mooney viscosity (ML1 + 4, 100 ° C) 45

‧EPDM: Trade name "EPT 4070", manufactured by Mitsui Chemicals, 56% by mass of ethylene, 8% by mass of ethylidene norbornene, and Mooney viscosity (ML1 + 4, 125 ° C) 47

‧SBR: Trade name "Nipol 1502", manufactured by Zeon Japan, emulsion polymerization SBR, 23.5 mass% styrene bond, Mooney viscosity (ML1 + 4, 100 ° C) 52

‧CR: Trade name "Denka Chloroprene S-41", manufactured by Denka Chemical Industries, non-sulfur modified chloroprene rubber, Mooney viscosity (ML1 + 4, 125 ° C) 47

‧Glycol: made by Japan Catalyst Corporation

‧Diethylene glycol: made by Japan Catalyst Corporation

‧Glycerin: made by Sakamoto Pharmaceutical Co., Ltd.

‧1,2,6-hexanetriol: manufactured by Tokyo Chemical Industry Co., Ltd.

‧Diglycerin: made by Sakamoto Pharmaceutical Co., Ltd.

‧Sorbitol: Made by Kao Corporation

‧Polyglycerol A: Trade name: Polyglycerin # 310, molecular weight 330, manufactured by Sakamoto Pharmaceutical Co., Ltd.

‧Polyglycerol B: Trade name: Polyglycerin # 500, molecular weight 500, made by Sakamoto Pharmaceutical Co., Ltd.

‧ Sulfur: manufactured by Hosei Chemical Industry Co., Ltd.

‧Vulcanization accelerator A: N-tertiary butyl benzothiazole-2-sulfenimidine, trade name "Nocceler NS-P", manufactured by Onai Shinko Chemical Industry Co., Ltd.

‧Vulcanization accelerator B: tetramethylthiuram monosulfide, trade name "Sanceler TS-G", manufactured by Sanxin Chemical Industry Co., Ltd.

‧Vulcanization accelerator C: diphenylguanidine, trade name "Soxinol D-G", manufactured by Sumitomo Chemical Co., Ltd.

‧Anti-scorch agent: N-cyclohexylthiophthalimide, manufactured by FLEXSYS

‧Carbon Black A: ISAF Carbon Black: Trade name "Show Black N220", manufactured by Showa Cabot

‧Carbon Black B: FEF-grade carbon black: Trade name "HTC # 100", manufactured by NSCC Carbon

‧Hard clay: trade name "Suprex Clay", manufactured by Kentucky Tennessy Clay Company

‧Zinc oxide: Zinc oxide type 3, manufactured by Zhengtong Chemical Industry Co., Ltd.

‧Magnesium Oxide: Trade name "Kyowamag 150", manufactured by Kyowa Chemical Industry Co., Ltd.

‧Stearic acid: made by Japan Oil & Fats Co., Ltd.

‧Ozone-Resistant: Trade name "Ozonone 6C", manufactured by Seiko Chemical Co., Ltd.

‧Plasticizer: Dioctyl adipate, trade name "DIACIZER DOA", manufactured by Mitsubishi Kasei Vinyl

‧Processing oil: Aromatic oil, trade name "A-OMIX", manufactured by Sankyo Petrochemical Industry Co., Ltd.

<2. Evaluation of rubber composition>

A tube-like shape having a rubber outer layer composed of each rubber composition obtained in Examples 1 to 11 and Comparative Examples 1 to 10 and a reinforcing layer composed of a brass-plated wire A test piece was produced in the following manner.

First, a braided wire was wound into a sheet shape on a mandrel with an outer diameter of 34 mm to form a reinforcing layer. Next, an unvulcanized sheet having a thickness of 2.5 mm prepared from each of the obtained rubber compositions was bonded to a reinforcing layer to obtain an unvulcanized hose-shaped test piece. Then, a vulcanized adhesive tape (protective cloth) made of nylon 66 was wound and vulcanized so as to cover the outside of the unvulcanized hose-shaped test piece.

The vulcanization was performed under the following two conditions, and the adhesive strength and rubber adhesion of the obtained tube-shaped vulcanization test piece were evaluated. Adhesive strength and rubber adhesion are average values of values measured 10 times each.

‧Vulcanization condition 1: An unvulcanized hose-shaped test piece made using the rubber composition immediately after kneading is vulcanized (steam vulcanized) in a steam tank at 142 ° C for 90 minutes.

‧Vulcanization condition 2: The unvulcanized hose-shaped test piece prepared using the rubber composition immediately after kneading is vulcanized (oven vulcanization) in an atmospheric pressure oven at 142 ° C for 135 minutes.

<Adhesion test 1>

For each of the hose-shaped vulcanization test pieces obtained in the above-mentioned vulcanization condition 1, the adhesive strength (kN / m) and rubber adhesion (%) were evaluated. Here, the so-called adhesive strength (kN / m) is the magnitude (kN) of the force per unit width (m) required to peel the outer rubber layer from the interface between the outer rubber layer and the reinforcing layer at a peeling speed of 50 mm / min. ). Here, the rubber adhesion is a ratio of the rubber layer on the outer side of the hose-shaped vulcanized test piece remaining on the surface of the reinforcing layer, and the area ratio of the residual rubber layer to the entire surface area of the reinforcing layer is expressed as a percentage. The values of the adhesive strength (kN / m) and rubber adhesion (%) are average values after 10 measurements. The evaluation results are shown in Tables 3 and 4. The evaluation results are expressed as an index based on the result of 100 adhesion tests of Comparative Example 1.

<Adhesion test 2>

Except that each of the tube-shaped vulcanization test pieces obtained in the vulcanization condition 2 was used, the adhesiveness was evaluated in the same manner as in the adhesiveness test 1.

<Adhesion Test 3>

Each of the hose-shaped vulcanization test pieces obtained in the vulcanization condition 1 was stored in a constant temperature and humidity tank at 50 ° C. and 95% relative humidity (% RH) for one week, and the adhesion was evaluated in the same manner as in the adhesion test 1.

<Adhesion Test 4>

Each tube-shaped vulcanization test piece obtained in the vulcanization condition 2 was After storage in a constant temperature and humidity tank at 95 ° C and 95% relative humidity (% RH) for one week, the adhesion was evaluated in the same manner as in the adhesion test 1.

As shown in Tables 3 and 4, the polyol is compounded such that the hydroxyl equivalent becomes a predetermined amount relative to the diene polymer. In Examples 1 to 11 of the Examples, excellent adhesion evaluation was obtained regardless of the vulcanization method of the steam vulcanization method and the oven vulcanization method. On the other hand, when a polyol compound is not formulated, sufficient adhesive strength can be obtained in the steam vulcanization method, but it can be seen that the adhesive strength is significantly deteriorated in the oven vulcanization method (Comparative Example 1). In addition, when the hydroxyl equivalent of the polyhydric alcohol compound is less than a predetermined range, sufficient adhesion strength can be obtained in the steam curing method, but it can be seen that in the oven curing method, the adhesive strength is significantly deteriorated especially after storage in a hot and humid state ( Comparative Examples 2, 9). In addition, when the hydroxyl equivalent of the polyol compound is more than a predetermined range, sufficient adhesive strength can be obtained in the oven vulcanization method, but it can be seen that the adhesive strength is significantly deteriorated in the vapor vulcanization method (Comparative Examples 3, 4, and 10). . These results can be considered because the balance of the catalytic function of the bond reaction between sulfur and the metal surface caused by the polyol compound is deteriorated. In addition, when sulfur is more than a predetermined range, it can be seen that the adhesion evaluation tends to decrease regardless of the curing method (Comparative Example 5). In addition, when sulfur is less than a predetermined range, it can be seen that the adhesion strength is significantly deteriorated regardless of the curing method (Comparative Example 6). These results can be considered because the balance of the catalytic function of the bond reaction between sulfur and the metal surface caused by the polyol compound is deteriorated. In addition, when a polyol compound having a molecular weight exceeding 300 is used, it is known that the adhesive strength is deteriorated especially in the vapor vulcanization method (Comparative Examples 7 and 8). This result can be considered because the molecular weight of the polyhydric alcohol compound is too large, and therefore, in the rubber composition, the catalyst function of the bond reaction between sulfur and the metal surface is not exhibited.

Claims (7)

A rubber composition characterized in that it contains 0.5 parts by mass or more and 4 parts by mass or less of 100 parts by mass of a diene polymer capable of being vulcanized with sulfur, and 0.004 mol or more and 0.17 mol or less. A polyol compound having a molecular weight of 300 or less; and the aforementioned polyol compound is a compound represented by the following general formula (1), (In formula (1), R ₁ represents a hydrogen atom or a mono- or polyhydroxyalkyl group having 1 or more and 5 or less carbon atoms that can contain an ether bond and a branch, and R ₂ represents 1 or more carbon atoms that can contain an ether bond and a branch and 5 or less mono or polyhydroxyalkyl). A rubber composition metal laminate includes a reinforcing layer having a metal surface and a rubber layer containing the rubber composition according to claim 1 provided on the metal surface. The rubber composition metal laminate according to claim 2, wherein the aforementioned metal surface is formed by brass plating. For example, the rubber composition metal laminate of claim 2, wherein the reinforcing layer has a braid structure or a spiral structure obtained by weaving a wire. A vulcanized rubber product obtained by using the rubber composition as claimed in claim 1. A vulcanized rubber product which vulcanizes the aforementioned rubber layer of the rubber composition metal laminate according to any one of claims 2 to 4 in the presence of sulfur and adheres to the aforementioned reinforcing layer. The vulcanized rubber product of claim 6 is a hose.