JP6464600B2 - Rubber composition, rubber composition metal laminate, and vulcanized rubber product - Google Patents

Description

  The present invention relates to a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product, and particularly relates to a rubber composition containing a rosin ester, a rubber composition metal laminate, and a vulcanized rubber product.

  Conventionally, a rubber composition for coating a steel cord used for a belt layer of a pneumatic radial tire as a composite of a rubber layer and a metal has been proposed (see, for example, Patent Document 1). In this rubber composition, by containing a predetermined amount of organic acid cobalt and rosin, adhesion to a steel cord is imparted and water-resistant adhesion is improved.

JP 2010-59234 A

  By the way, as a composite of a rubber composition and a metal, there are a hydraulic hose and a high-pressure hose in which a reinforcing layer whose surface is brass-plated is sandwiched between a pair of rubber layers. These hose production methods include a steam vulcanization method in which the rubber composition is heated and vulcanized with steam, and a hot air vulcanization method (oven vulcanization method) in which the rubber composition is heated and vulcanized in an oven. There is. The oven vulcanization method can continuously vulcanize, so that the hose productivity can be improved.

  However, when a rubber composition is vulcanized by a hot-air vulcanization method, water evaporation is significant during vulcanization, and sufficient adhesion between the rubber layer and the reinforcing layer may not always be obtained. For this reason, even when vulcanized by a hot-air vulcanization method, a rubber composition that can obtain a rubber layer excellent in adhesiveness with a reinforcing layer is desired.

  The present invention has been made in view of such circumstances, and even when vulcanized by a hot-air vulcanization method, a rubber composition excellent in adhesion to a reinforcing layer, and a rubber composition metal laminate And to provide a vulcanized rubber product.

  The rubber composition of the present invention comprises 100 parts by mass of a sulfur vulcanizable diene polymer, 0.5 to 1.5 parts by mass of sulfur, and 0.1 to 20 parts by mass of rosin ester. Part or less.

  In the rubber composition of the present invention, the diene polymer has a chloroprene rubber content of 40% by mass to 100% by mass and a styrene butadiene rubber content of 0% by mass to 60% by mass. Preferably there is.

  In the rubber composition of this invention, it is preferable that the softening point of the said rosin ester is 50 degreeC or more and 150 degrees C or less.

  In the rubber composition of the present invention, the acid value of the rosin ester is preferably 50 or less.

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

  In the rubber composition metal laminate of the present invention, it is preferable that the metal surface is subjected to brass plating.

  In the rubber composition metal laminate of the present invention, the reinforcing layer preferably has a braided structure in which wires are knitted and / or a spiral structure.

  The vulcanized rubber product of the present invention is characterized in that the rubber layer of the rubber composition metal laminate is vulcanized and bonded to the reinforcing layer.

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

  In the vulcanized rubber product of the present invention, the hose is preferably vulcanized by a hot air vulcanization method.

  According to the present invention, a rubber composition, a rubber composition metal laminate, and a vulcanized rubber product having excellent adhesion to a metal surface of a reinforcing layer are realized even when vulcanized by a hot air vulcanization method. it can.

FIG. 1 is a schematic perspective view showing an example of a hose according to an embodiment of the present invention. FIG. 2 is an explanatory diagram of a manufacturing process of a hose using the rubber composition according to the embodiment of the present invention. FIG. 3 is an explanatory diagram of a hose vulcanization process 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 around a mandrel that is fed into a vulcanizing apparatus in a hose manufacturing process 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 accompanying drawings. In addition, this invention is not limited to the following embodiment, It can implement by changing suitably.

  The rubber composition according to the present embodiment includes 100 parts by mass of a sulfur vulcanizable diene polymer, 0.5 parts by mass or more and 1.5 parts by mass or less of sulfur, and 0.1 parts by mass of rosin ester. 20 parts by mass or less.

  According to this rubber composition, since a predetermined amount of rosin ester is contained in the sulfur vulcanizable diene polymer, at least a part of the rosin ester is hydrolyzed during vulcanization by the hot air vulcanization method. As a result, the reaction between the metal surface of the reinforcing layer and sulfur is promoted based on the alcohol component and the carboxylic acid component generated by hydrolysis, so that the adhesive strength between the rubber composition after vulcanization and the metal surface of the reinforcing layer is increased. Will improve. Hereinafter, various components of the rubber composition according to the present embodiment will be described in detail.

<Diene polymer>
As the diene polymer, a polymer containing chloroprene rubber (CR) is preferably used. Chloroprene rubber (CR) is a homopolymer of a chloroprene monomer (hereinafter referred to as “chloroprene monomer”) or a chloroprene monomer and one or more other monomers copolymerizable therewith. It is a copolymer obtained by polymerizing a mixture.

  Chloroprene rubber is classified into a sulfur-modified type, a mercaptan-modified type, and a xanthogen-modified type depending on the type of molecular weight regulator. Any modified type can be used as the chloroprene rubber. Among these, the mercaptan-modified type and the xanthogen-modified type are preferable when more heat resistance is required because the polymer itself has better heat resistance than the sulfur-modified type.

  The sulfur-modified type chloroprene rubber is a polymer obtained by copolymerizing sulfur and a chloroprene monomer or a chloroprene monomer with thiuram disulfide to adjust to a predetermined Mooney viscosity.

  The mercaptan-modified type chloroprene rubber uses an alkyl mercaptan such as n-dodecyl mercaptan, tert-dodecyl mercaptan, octyl mercaptan as a molecular weight regulator.

  The xanthogen-modified chloroprene rubber uses an alkyl xanthogen compound as a molecular weight regulator. There is no restriction | limiting in particular as an alkylxanthogen compound, According to the objective, it can select suitably. Examples of the alkyl xanthogen compound include dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, diisobutyl xanthogen disulfide, and the like.

  The amount of the alkyl xanthogen compound used is not particularly limited as long as the molecular weight (or Mooney viscosity) of the chloroprene rubber is appropriate, depending on the purpose (the structure of the alkyl group and the target molecular weight). It can be selected appropriately. The amount of the alkyl xanthogen compound used is preferably 0.05 parts by weight or more and 5.0 parts by weight or less, and 0.3 parts by weight or more and 1.0 parts by weight with respect to 100 parts by weight of the chloroprene monomer or chloroprene monomer. Less than the mass part is more preferable.

  As the diene polymer, a sulfur vulcanizable diene polymer other than chloroprene rubber may be used within the range where the effects of the present invention are exhibited. Here, sulfur vulcanizable means the property that a crosslinked structure is formed through sulfur. Other diene polymers include, for example, natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), and ethylene-propylene-diene rubber. (EPDM). By using these, various physical properties for hoses required for the rubber composition can be exhibited at a high level. These diene polymers may be used alone or in combination of two or more.

  In the present embodiment, from the viewpoint of heat resistance of the rubber composition and adhesion to the metal surface of the reinforcing layer, the content of chloroprene rubber (CR) is 40% by mass to 100% by mass, and styrene butadiene It is preferable to use a rubber (SBR) content of 0% by mass to 60% by mass.

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

<Rosin ester>
The rubber composition according to the present embodiment contains a predetermined amount of rosin ester with respect to the diene copolymer. By containing this rosin ester, the rosin ester reacts with moisture in the rubber composition and decomposes into a carboxylic acid component and an alcohol component when heated and vulcanized by a hot air vulcanization method. As a result, the reaction between the metal surface of the reinforcing layer and sulfur is promoted based on the alcohol component and the carboxylic acid component generated by hydrolysis, so that the adhesive strength between the rubber composition after vulcanization and the metal surface of the reinforcing layer is increased. Will improve. Therefore, even when vulcanized by the hot air vulcanization method, it is possible to improve the adhesion of the reinforcing layer to the metal surface.

  The rubber composition according to the present embodiment contains a rosin ester. This rosin ester is obtained by esterifying a rosin by an esterification reaction between rosin and an alcohol compound or an epoxy compound. As the rosin ester, various rosin esters can be used within the scope of the effects of the present invention, and examples thereof include rosin esters such as ethylene glycol, diethylene glycol, glycerin and pentaerythritol.

  There is no restriction | limiting in particular as an alcohol compound used as a raw material of rosin ester, Various well-known polyhydric alcohol is mentioned. Examples of the alcohol compound include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentanediol. , By adding ethylene oxide or propylene oxide to saturated alcohol compounds such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol and dipropylene glycol, unsaturated dihydric alcohol, bisphenol A Obtained dihydric alcohols, trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, hexahydric alcohols such as dipentaerythritol, ethyl Ethylene oxide in which the aliphatic polyhydric alcohols such as glycol or glycerol as an initiator, and the like polyether polyols such as polymers and copolymers such as propylene oxide and tetrahydrofuran. These alcohol compounds may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as an epoxy compound used as a raw material of rosin ester, Various well-known mono epoxy compounds, a polyhydric epoxy compound, etc. are mentioned.

  Examples of monoepoxy compounds include alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, versatic acid glycidyl esters, glycidyl monocarboxylic acid glycidyl esters Examples thereof include esters, styrene oxide, and cyclohexene oxide.

  Examples of the diepoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. Acyclic aliphatic diglycidyl ether such as polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2,2-bis (4-hydroxyphenyl) Propane diglycidyl ether, bisphenol A high molecular weight epoxy resin, bis (4- Roxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethane diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl ether, 3,3 ′, 5,5′- Aromatic or cycloaliphatic diglycidyl ethers such as tetramethyl-4,4′-dihydroxybiphenyl diglycidyl ether, 2,2-bis (4- (β-hydroxypropoxy) phenyl) propane diglycidyl ether, resorcinol diglycidyl ether , Aromatic or cycloaliphatic diglycidyl esters such as diglycidyl phthalate anhydride, diglycidyl hexahydro anhydride, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexane And diepoxy compounds such as cycloaliphatic cyclic oxiranes such as xenedioxide.

  Examples of the triepoxy compound include trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, trishydroxyethyl isocyanurate triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trimellitic acid triglycidyl ester, and the like. Is mentioned. Examples of the tetraepoxy compound include 1,1,2,2-tetra (4-hydroxyphenyl) ethanetetraglycidyl ether, bisresorcinol tetraglycidyl ether, and the like. Examples of other polyepoxy compounds include sorbitol polyglycidyl ether, polyglycidyl ether of phenol novolac type resin, and the like. These epoxy compounds may be used individually by 1 type, and may use 2 or more types together.

  A commercially available product can be used as the rosin ester. Examples of commercially available rosin esters include “Harimak (registered trademark) R-80” (manufactured by Harima Kasei Co., Ltd.), and trade name “Harimak (registered trademark) M-453” (manufactured by Harima Chemical Co., Ltd.).

  The rosin ester preferably has a softening point of 50 ° C. or higher, more preferably 60 ° C. or higher, and 70 ° C. or higher from the viewpoint of obtaining a rubber composition having excellent adhesion to the metal surface of the reinforcing layer. Are more preferable, those having a temperature of 150 ° C. or lower are preferable, those having a temperature of 140 ° C. or lower are more preferable, and those having a temperature of 130 ° C. or lower are still more preferable. Considering the above, the softening point of the rosin ester is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 140 ° C. or lower, and further preferably 70 ° C. or higher and 130 ° C. or lower. In the present embodiment, the softening point is a value measured by a ring and ball softening point measuring device (JIS K 6220-1: 2001).

  The rosin ester preferably has an acid value of 5 or more, more preferably 10 or more, more preferably 15 or more, more preferably 50 or less, and more preferably less than 35. Preferably, it is 30 or less. Considering the above, the acid value of the rosin ester is preferably 5 or more and 50 or less, more preferably 10 or more and 35 or less, and still more preferably 15 or more and 30 or less. In the present embodiment, the acid value is a value measured by neutralization titration method or potential titration method (JIS K 0070: 1992).

  The blending amount of the rosin ester is 0.1 parts by mass or more with respect to 100 parts by mass of the diene polymer from the viewpoint of obtaining a rubber composition having excellent adhesion to the metal surface of the reinforcing layer. 5 parts by mass or more is preferable, 1.0 part by mass or more is more preferable, 3.0 parts by mass or more is further preferable, 20 parts by mass or less is preferable, 15 parts by mass or less is preferable, and 10 parts by mass or less is more preferable. 7 parts by mass or less is more preferable. Considering the above, the blending amount of the rosin ester is 0.1 parts by mass or more and 20 parts by mass or less, and preferably 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the diene polymer. 1.0 mass part or more and 10 mass parts or less are more preferable, and 3.0 mass parts or more and 7.0 mass parts or less are still more preferable.

<Other rosins>
In the rubber composition which concerns on this Embodiment, you may contain other rosins in the range with the effect of this invention. Examples of other rosins include natural rosin, polymerized rosin, hydrogenated rosin, maleated rosin, disproportionated rosin, and derivatives thereof.

  Other rosins include, for example, unmodified rosin (natural rosin) such as gum rosin, wood rosin and tall rosin, and unmodified rosin such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid and acrylic acid. Unsaturated carboxylic acid-modified rosin modified with saturated carboxylic acid (for example, maleated rosin and acrylated rosin), hydrogenated rosin hydrogenated unmodified rosin (hydrogenated rosin), polymerized rosin polymerized unmodified rosin, Examples thereof include a disproportionated rosin obtained by disproportionating an unmodified rosin, a phenol-modified rosin obtained by modifying an unmodified rosin with a phenol, and a modified rosin (rosin derivative) such as a formylated rosin obtained by subjecting an unmodified rosin to formalin. These modified rosins also include rosin-containing diols (rosin diols) each having two rosin skeletons and two hydroxyl groups in the molecule.

<Vulcanizing agent>
The rubber composition according to the present embodiment contains sulfur as a vulcanizing agent. Sulfur includes powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface treated sulfur, and insoluble sulfur.

  The sulfur content is 0.5 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer. When the sulfur content is 0.5 parts by mass or more and 1.5 parts by mass or less, a rubber composition having excellent heat resistance and excellent adhesion between the rubber layer and the reinforcing layer using the rubber composition is obtained. It is done. The sulfur content is preferably 0.55 parts by mass or more, more preferably 0.6 parts by mass or more, still more preferably 0.7 parts by mass or more, based on 100 parts by mass of the diene polymer. Part or more is more preferable, 1.3 parts by mass or less is preferable, 1.2 parts by mass or less is more preferable, 1.1 parts by mass or less is further preferable, and 1.0 part by mass or less is still more preferable. Considering the above, the sulfur content is preferably 0.55 parts by mass or more and 1.3 parts by mass or less, and 0.6 parts by mass or more and 1.2 parts by mass or less with respect to 100 parts by mass of the diene polymer. More preferably, 0.7 parts by mass or more and 1.1 parts by mass or less are more preferable, and 0.8 parts by mass or more and 1.0 parts by mass or less are further more preferable.

  The rubber composition according to the present embodiment may contain a vulcanizing agent other than sulfur as long as the effects of the present invention are achieved. Examples of vulcanizing agents other than sulfur include vulcanizing agents such as sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, and quinone dioxime. These may be used alone or in combination of two or more. Examples of the sulfur-based vulcanizing agent include organic sulfur-containing compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dimorpholine disulfide, and alkylphenol disulfide. it can.

  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).

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

<Vulcanization accelerator>
The rubber composition according to the present embodiment preferably contains a vulcanization accelerator. Vulcanization accelerators include thiuram vulcanization accelerators, guanidine vulcanization accelerators, sulfenamide vulcanization accelerators, thiourea vulcanization accelerators, aldehyde-ammonia vulcanization accelerators, and aldehyde-amines. Examples thereof include a system vulcanization accelerator, a thiazole vulcanization accelerator, a dithiocarbamate vulcanization accelerator, and a xanthate vulcanization accelerator. These may be used alone or in combination of two or more.

  Examples of thiuram vulcanization accelerators include dipentamethylene thiuram tetrasulfide, tetramethyl thiuram monosulfide (TS), tetramethyl thiuram disulfide (TT), tetraethyl thiuram disulfide (TETD), and tetrabutyl thiuram disulfide (TBTD). , Tetrabenzylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.

  Examples of the guanidine vulcanization accelerator include N, N′-diphenylguanidine, N, N′-diortolylguanidine and the like.

  Examples of the sulfenamide-based vulcanization accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), Nt-butyl-2-benzothiazolylsulfenamide (NS), N- Examples thereof include oxydiethylene-2-benzothiazolylsulfenamide, N, N-diisopropyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamide.

  Examples of the thiourea vulcanization accelerator include ethylene thiourea (2-mercaptoimidazoline), N, N′-diethylthiourea, trimethylthiourea, N, N′-dibutylthiourea, and the like.

  The content of the vulcanization accelerator is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the diene polymer from the viewpoint of adhesion between the reinforcing layer and the rubber layer containing the rubber composition. 75 parts by mass or more is more preferable, 1.0 part by mass or more is further preferable, 3.0 parts by mass or less is preferable, 2.5 parts by mass or less is more preferable, and 2.0 parts by mass or less is still more preferable.

[Other additives]
Moreover, the rubber composition can contain other additives as necessary within the range where the effects of the present invention are exhibited. Other additives include, for example, fillers, plasticizers, softeners, anti-aging agents, organic activators, antioxidants, antistatic agents, flame retardants, crosslinking accelerators, vulcanization retarders, ozone degradation Inhibitors, aroma oils and adhesion aids.

  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, Examples include mica (mica) and diatomaceous earth. These may be used alone or in combination of two or more.

  The rubber composition according to the present embodiment preferably contains carbon black. When carbon black is contained, rubber performance such as tensile strength and abrasion resistance of rubber is improved. Examples of carbon black include furnace black, acetylene black, ketjen black, and thermal black.

  As furnace black, for example, SAF (Super Abrasion Furnace), ISAF (Intermediate Super Abrasion Furnace), IISAF-HS (Intermediate ISAF-High Fur Eure, FAF, High AF, High AF, High AF). Examples thereof include “Purpose Furnace” and SRF (Semi-Reinforcing Furnace).

  Examples of the thermal black include FT (Fine Thermal) and MT (Medium Thermal).

  The carbon black is preferably ISAF grade carbon black, HAF grade carbon black, FEF grade carbon black, GPF grade carbon black, SRF grade carbon black, FEF grade carbon black, GPF grade from the viewpoint of reinforcement and rubber extrusion processability. Carbon black and SRF grade carbon black are more preferable. These may be used alone or in combination of two or more.

  Examples of the silica 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 hard clay, waxite 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 , Trioctyl phosphate, trimellitic acid ester, propylene glycol adipate polyester, butylene glycol adipate polyester, naphthene oil, and the like. These may be used alone or in combination of two or more.

  Specific examples of the softener include aroma oil, naphthene oil, paraffin oil, petroleum resin, vegetable oil, and liquid rubber. These may be used alone or in combination of two or more.

  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) and the like. These may be used alone or in combination of two or more.

  Examples of the organic active agent 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 hydrophilic compounds such as quaternary ammonium salts, 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. As the rubber auxiliary, for example, zinc white, magnesium oxide, 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, acetylsalicylic acid, N-nitroso-diphenylamine, N-nitroso-phenyl-β-naphthylamine, and N-nitroso-trimethyl-dihydroquinoline. Examples thereof include nitroso compounds such as polymers, halides such as trichloromelanin, 2-mercaptobenzimidazole, and N- (cyclohexylthio) phthalimide (PVI). These may be used alone or in combination of two or more.

  Examples of the adhesion assistant include 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, monomethylol melamine, monomethylol urea, ethylene maleimide, cobalt naphthenate, cobalt stearate, cobalt versatate, and cobalt dodecanoate. These may be used alone or in combination of two or more.

<Method for producing rubber composition>
The rubber composition according to the present embodiment can be produced by a conventionally known production method. As a manufacturing method of the rubber composition according to the present embodiment, for example, first, 100 parts by mass of a sulfur vulcanizable diene polymer, 0.5 parts by mass to 1.5 parts by mass of sulfur, and rosin 0.1 parts by mass or more and 20 parts by mass or less of an ester and, if necessary, other diene polymers and polymers other than diene polymers and the above various additives are blended. And the manufacturing method knead | mixed using a Banbury mixer, closed mixers, such as a kneader, kneading roll machines, such as a roll, an extruder, a twin screw extruder, etc. are mentioned.

[Rubber composition metal laminate]
The rubber composition metal laminate according to the present embodiment is a laminate of the rubber composition and a wire reinforcing layer whose surface is metal-plated. As this laminated body, hoses, such as a high pressure hose and a hydraulic hose, are mentioned, for example. FIG. 1 is a partially broken perspective view showing an example of a hose according to the present embodiment. As shown in FIG. 1, the hose 1 is formed in a cylindrical shape, and includes an inner rubber layer 11 through which fluid passes, a reinforcing layer 12 provided outside the inner rubber layer 11, and an outer side of the reinforcing layer 12. And an external 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 bonded and fixed by vulcanization of the inner rubber layer 11 and the outer rubber layer 13.

<Rubber layer>
As described above, the inner rubber layer 11 and / or the outer rubber layer 13 are rubber layers using the rubber composition according to 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 according to the above embodiment. The inner rubber layer 11 is preferably formed using a rubber composition mainly composed of acrylonitrile butadiene rubber (NBR) having excellent oil resistance.

  For example, the thickness of the internal rubber layer 11 is preferably 0.2 mm or greater and 4.0 mm or less, and more preferably 0.5 mm or greater and 2.0 mm or less. Similarly, the thickness of the external rubber layer 13 is preferably 0.2 mm or greater and 4.0 mm or less, and more preferably 0.5 mm or greater and 2.0 mm or less.

<Reinforcing layer>
The reinforcing layer 12 is a wire blade in which a steel wire is knitted, and the surface of the wire is brass-plated. This is a layer provided between the internal rubber layer 11 and the external rubber layer 13 from the viewpoint of maintaining the strength of the hose 1. In the example shown in FIG. 1, the reinforcing layer 12 is a single layer, but a plurality of reinforcing layers 12 in which an intermediate rubber layer is disposed between the layers may be provided. In addition to the wire blade, the reinforcing layer 12 may be formed as a spiral wire in which a steel wire rod is spirally wound around the inner rubber layer 11. The material forming the reinforcing layer 12 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 hose or the like, the reinforcing layer 12 is preferably formed by a wire blade.

  Examples of the wire material include piano wire (carbon steel), hard steel wire, and stainless steel wire. As the wire material, piano wire (carbon steel) and hard steel wire are particularly preferable from the viewpoint of workability and strength.

  Since the reinforcing layer 12 is excellent in adhesiveness, it is preferable that the surface is metal-plated in order to enhance the adhesiveness with the rubber layer. This metal plating is a piano wire and a hard steel wire coated with brass (brass). In brass coating, copper is plated on the steel wire and zinc is plated on the copper and a heat diffusion treatment is applied to form the brass coating.

<Vulcanized rubber products>
The rubber composition metal laminate of the rubber composition and the reinforcing layer 12 is crosslinked, that is, vulcanized in the presence of sulfur, so that the rubber molecules forming the inner rubber layer 11 and the outer rubber layer 13 are spaced apart from each other. Cross-linked by sulfur. By this crosslinking, elasticity and tensile strength are imparted to the inner rubber layer 11 and the outer rubber layer 13, and the metal (copper, zinc) and sulfur constituting the brass coating are bonded at the interface with the reinforcing layer 12. The inner rubber layer 11 and the outer rubber layer 13 are bonded to the reinforcing layer 12.

  Sulfur is preferably blended together with other materials when forming a compound as a rubber composition. In addition, in the blending of sulfur, molecular chains forming a diene polymer with sulfur are cross-linked by sulfur, and metal (copper, zinc) and sulfur at the interface between the inner rubber layer 11 and the outer rubber layer 13 and the reinforcing layer 12 are combined. As long as the inner rubber layer 11, the outer rubber layer 13 and the reinforcing layer 12 are bonded together by bonding to each other, it is not limited to the blending at the time of compound preparation.

  Examples of the vulcanization method include a method in which the rubber composition is heated at a predetermined temperature for a predetermined time in the presence of sulfur. 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 can be suitably used as a hose or the like. As a method for manufacturing hoses, for example, 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 a rubber composition metal laminate is covered with a nylon cloth or the like And an oven vulcanization method (hot air vulcanization method) for vulcanizing in a hot air drying furnace. In general, the steam vulcanization method is a batch process, and the oven vulcanization method is a continuous process. As a method for producing the hose, an oven vulcanization method which is a continuous treatment is preferable.

<Method for producing vulcanized rubber product>
Below, the manufacturing method of the vulcanized rubber product which concerns on this Embodiment is demonstrated. Here, a case where a hose is manufactured as a vulcanized rubber product will be described as an example.

  With reference to FIG.2 and FIG.3, the manufacturing method of the hose which concerns on this Embodiment is demonstrated. FIG. 2 is an explanatory view of a manufacturing process of a hose using the rubber composition according to the embodiment of the present invention, and FIG. 3 is a vulcanization of the hose using the rubber composition according to the embodiment of the present invention. It is explanatory drawing of a process.

<Hose manufacturing process>
As shown in FIG. 2, the rubber hose has a rubber material extrusion process (step S101) for forming the internal rubber layer 11, a reinforcement layer 12 knitting process (step S102), and an external rubber layer 13 extrusion / vulcanization process (step). S103) and the mandrel 101 extraction step (step S104). The manufactured rubber hose is packed and shipped through a water pressure inspection and an inspection winding process.

  First, in step S <b> 101, the unvulcanized inner rubber layer 11 is coated on the outer peripheral surface of the mandrel 101 fed from the unwinder 100 by the first extruder 102. The hose 103 covered with the internal rubber layer 11 is wound around the winding / unwinding machine 104.

  Next, in step S102, the hose 106, in which the reinforcing layer 12 is formed by braiding with the braiding machine 105 so as to cover the internal rubber layer 11 constituting the hose 103 fed out from the winding and unwinding machine 104, is unwound and unwound. Wind up on machine 107. A metal wire is used for the cord of the reinforcing layer 12. As the metal wire, a steel wire plated with brass is used in order to improve the adhesion to rubber. The reinforcing layer 12 may be formed by winding a metal wire in a spiral around the inner rubber layer 11 formed around the mandrel 101.

  Next, in step S103, the unvulcanized outer rubber layer 13 is covered by the second extruder 108 on the reinforcing layer 12 of the hose 106 fed out from the winding unwinder 107 to form the hose body 109. Then, the formed hose body 109 is wound around the winder 110. In the present embodiment, the hose 112 vulcanized by performing a vulcanization process by the vulcanizer 111 while the hose body 109 is wound around the winder 110 after leaving the second extruder 108. Although it is wound up by the winder 110, the vulcanization step may be provided after the hose body 109 is wound up by the winder 110. Further, a wrapping device 113 and an unwrapping device 114 for detaching a protective cloth such as a nylon cloth from the hose body 109 are provided before and after the vulcanizing device 111. In FIG. 2, the hose 115 before vulcanization in which the nylon cloth is wound by the lapping device 113 becomes the hose 116 after vulcanization and before removing the nylon cloth. The vulcanization process will be described later.

  Next, in step S104, after vulcanization, the mandrel 101 is extracted from the unwrapped hose 116 unwound from the winder 110 by the mandrel extraction device 117, and the hose 118 is completed.

<Vulcanization process>
As shown in FIG. 3, a nylon cloth 119 is wound around the hose body 109 exiting the second extruder 108 by a lapping device 113. The hose body 109 covered with the nylon cloth 119 is carried into the vulcanizer 111. The vulcanizing device 111 is a hot air circulation type continuous vulcanizing device that advances vulcanization with hot air 120. This vulcanization method is an oven vulcanization method.

  FIG. 4 is a partial cross-sectional view for explaining an example of the layer structure around the mandrel 101 to be charged into the vulcanizer. As shown in FIG. 4, an inner rubber layer 11 is formed around the mandrel 101, a reinforcing layer 12 is formed around the inner rubber layer 11, and an outer rubber layer 13 is formed around the inner rubber layer 11. A nylon cloth 119 is wound around the outer rubber layer 13 and heated in this state to proceed with the vulcanization process.

  As described above, the vulcanization temperature is preferably 130 ° C. or higher and 180 ° C. or lower, and the vulcanization time, that is, the vulcanization time in the vulcanizer 111 is preferably 30 minutes or longer and 240 minutes or shorter. In this temperature range and vulcanization time, a hose having good adhesion between the internal rubber layer 11 and the external rubber layer 13 and the reinforcing layer 12 can be obtained. Here, by forming the inner rubber layer 11 and / or the outer rubber layer 13 using the rubber composition according to the above embodiment, the inner rubber layer 11 and / or the outer rubber layer 13 and the metal reinforcing layer 12 are formed. A hose with good adhesiveness can be produced.

  In addition, according to the rubber composition, moderate moisture can be stably held in the composition until immediately before vulcanization, so even in the oven vulcanization method with large moisture evaporation, it suppresses adhesion failure and deterioration of adhesion due to lack of moisture. it can. However, it goes without saying that the rubber composition according to the above-described embodiment can be suitably used for 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, a vulcanized rubber product can also be manufactured by the method of bonding, after manufacturing a rubber layer and a reinforcement layer by another process.

  The hose manufactured by the manufacturing method according to the present embodiment can be applied to various uses. As a use of the hose, for example, it can be suitably used as an air conditioner hose for automobiles, a power steering hose, a hydraulic hose used for a hydraulic system of a construction vehicle, and the like.

  In the present embodiment, the 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 a conveyor belt. The same can be used in the body.

  As described above, according to the rubber composition metal laminate, the vulcanized rubber product, and the method for producing the vulcanized rubber product, the adhesiveness between the rubber layer and the reinforcing layer is ensured even in the continuous production method by the oven vulcanization method. A good vulcanized rubber product 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 described in more detail with reference to examples made to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples and comparative examples.

<Preparation of rubber composition>
( Reference Example 1)
Chloroprene rubber (trade name “Denka Chloroprene S-41”, manufactured by Denki Kagaku Kogyo Co., Ltd., mercaptan modified chloroprene rubber, Mooney viscosity (ML1 + 4, 125 ° C.) 47) 50% by mass and styrene butadiene rubber (trade name “Nipol 1502”, 5 parts by mass with respect to 100 parts by mass of a diene polymer containing 50 mass% of emulsion polymerization SBR, bound styrene content 23.5 mass%, Mooney viscosity (ML1 + 4,100 ° C.) 52, manufactured by Nippon Zeon Co., Ltd. Rosin A (rosin ester, trade name “Harimak (registered trademark) R-80”, manufactured by Harima Chemical Co., Ltd.), 0.75 parts by mass of sulfur (manufactured by Hosoi Chemical Co., Ltd.), and 0.75 parts by mass of vulcanization Accelerator A (tetramethylthiuram monosulfide, trade name “Sunseller TS-G”, manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.75 parts by mass Sulfur accelerator B (N, N′-diphenylguanidine, trade name “Soccinol DG”, manufactured by Sumitomo Chemical Co., Ltd.) and 45 parts by mass of carbon black A (FEF grade carbon black: trade name “HTC # 100”, Nippon Steel Chemical Co., Ltd.), 45 parts by mass of carbon black B (ISAF grade carbon black: trade name “Show Black N220”, manufactured by Showa Cabot), 20 parts by mass of naphthenic oil, and 10 parts by mass of aroma. Oil (trade name “A-OMIX”, manufactured by Sankyo Oil Chemical Co., Ltd.), 2 parts by weight of fatty acid ester (dioctyl adipate, trade name “DIACIZER DOA”, manufactured by Mitsubishi Kasei Vinyl), and 2 parts by weight of aging prevention Agent (trade name “Ozone Non 6C” manufactured by Seiko Chemical Co., Ltd.), 1.6 parts by mass of paraffin wax A, 2.4 parts by mass of paraffin wax B, 2 parts by mass of a vulcanization retarder, 5 parts by mass of zinc oxide (3 types of zinc oxide, manufactured by Shodo Chemical Industry Co., Ltd.) and 3 parts by mass of stearic acid (manufactured by NOF Corporation) were blended, and Banbury Kimi A rubber composition was prepared by kneading with a sir and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Example 1 )
A rubber composition in the same manner as in Reference Example 1, except that 5 parts by mass of rosin B (rosin ester, trade name “Harimak (registered trademark) M-453”, manufactured by Harima Chemical Co., Ltd.) was blended in place of rosin A. Were fabricated and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 1)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that rosin A was not blended. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 2)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 5 parts by mass of rosin C (gum rosin, trade name “Gum rosin WW”, manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A. . The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 3)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 5 parts by mass of rosin D (gum rosin, trade name “Gum rosin X”, manufactured by Harima Chemical Co., Ltd.) was blended in place of rosin A. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 4)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 5 parts by mass of rosin E (Tall rosin, trade name “Hartol R-WW”, manufactured by Harima Chemical Co., Ltd.) was used instead of rosin A. did. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 5)
A rubber composition in the same manner as in Reference Example 1 except that 5 parts by mass of rosin F (acrylic rosin, trade name “Harimak (registered trademark) T-80, manufactured by Harima Chemical Co., Ltd.)” was blended in place of rosin A. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 6)
A rubber composition was prepared in the same manner as in Reference Example 1, except that 5 parts by mass of rosin G (hydrogenated rosin, trade name “Halitak (registered trademark) F”, manufactured by Harima Chemical Co., Ltd.) was blended in place of rosin A. Fabricated and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 7)
A rubber composition was prepared in the same manner as in Reference Example 1 except that 5 parts by mass of rosin H (hydrogenated rosin, trade name “HIVEL (registered trademark)” manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A. Fabricated and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 8)
Rubber composition in the same manner as in Reference Example 1 except that 5 parts by mass of rosin I (polymerized rosin, trade name “Aradaim (registered trademark) R-95”, manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A. Products were made and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Comparative Example 9)
Rubber composition as in Reference Example 1, except that 5 parts by mass of rosin J (disproportionated rosin, trade name “Longis (registered trademark) R”, manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A Products were made and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

In addition, the detail of each component described in Table 1 is as follows.
CR: Trade name “Denka Chloroprene S-41”, manufactured by Denki Kagaku Kogyo Co., Ltd., mercaptan-modified chloroprene rubber, Mooney viscosity (ML1 + 4, 125 ° C.) 47
E-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
・ Rosin A: Rosin ester, trade name “Harimak (registered trademark) R-80”, manufactured by Harima Chemical Co., Ltd. ・ Rosin B: Rosin ester, trade name: “Harimak (registered trademark) M-453”, manufactured by Harima Chemical Co., Ltd. ・ Rosin C: Gum rosin, trade name “Gum rosin WW”, Arakawa Chemical Industries, Ltd./Rosin D: Gum rosin, trade name “Gum rosin X”, Harima Kasei Co., Ltd./Rosin E: tall rosin, trade name “Hartol R-WW”, Harima Kasei・ Rosin F: Acrylic rosin, trade name “Harimak (registered trademark) T-80”, manufactured by Harima Kasei Co., Ltd. ・ Rosin G: Hydrogenated rosin, trade name “Halitac (registered trademark) F, manufactured by Harima Chemical Co., Ltd.” Rosin H: hydrogenated rosin, trade name “Hyval (registered trademark)”, manufactured by Arakawa Chemical Industries, Ltd./Rosin I: polymerized rosin, trade name “Aradaim (registered trademark) R-95”, Made by Kawa Chemical Co., Ltd., Rosin J: Disproportionated rosin, trade name "Longis (registered trademark) R", made by Arakawa Chemical Co., Ltd., sulfur: made by Hosoi Chemical Co., Ltd. , Trade name "Sunseller TS-G", Sanshin Chemical Industry Co., Ltd., vulcanization accelerator B: N, N'-diphenylguanidine, trade name "Soccinol DG", Sumitomo Chemical Co., Ltd., carbon black A: FEF Grade carbon black, trade name “HTC # 100”, manufactured by Nippon Nihon Carbon Co., Ltd., Carbon Black B: ISAF grade carbon black: trade name “Show Black N220”, Showa Cabot Corporation, naphthen oil: trade name “Cosmolex H22 (YR) ”, manufactured by JX Nippon Mining & Energy Co., Ltd., aroma oil: trade name“ A-OMIX ”, manufactured by Sankyo Oil Chemical Co., Ltd., fatty acid ester: dioctyl adip Product name “DIACIZER DOA”, manufactured by Mitsubishi Kasei Vinyl Co., Ltd., anti-aging agent: product name “Ozone Non 6C”, manufactured by Seiko Chemical Co., Ltd., paraffin wax A: product name “OZOACE-0015A”, manufactured by Nippon Seiwa Co., Ltd. Paraffin wax B: Trade name “OZOACE-0037”, manufactured by Nippon Seiwa Co., Ltd., Vulcanization retarder: Trade name “Kyowa Mag 150”, manufactured by Kyowa Chemical Industry Co., Ltd./Zinc oxide: 3 types of zinc oxide, manufactured by Shodo Chemical Industry Co., Ltd.・ Stearic acid: NOF Corporation

<Measurement of acid value>
It measured based on JISK0700: 1992. The sample was dissolved in a solvent, and an acid value was determined by performing potentiometric titration with a potassium hydroxide ethanol solution using a potentiometric titrator.

<Measurement of softening point>
It measured based on JISK6220-1: 2001. When the sample is heated under test conditions, the temperature at which the sample falls down to a specified distance is determined.

<Adhesion test>
A rubber composition having the composition shown in Table 1 was kneaded according to a conventional method to produce a rectangular unvulcanized rubber sheet having a width of 120 mm, a length of 120 mm, and a thickness of 1.2 mm. Was evaluated for adhesion

(Adhesion evaluation)
Three sets of five brass plating wires with a diameter of 0.6 mm and a length of 100 mm arranged in one set were arranged on the surface of the prepared unvulcanized rubber sheet, and both ends thereof were attached with tape and fixed. Next, the fixed unvulcanized rubber sheet was vulcanized in a hot air vulcanizer at 143 ° C. for 135 minutes, and then the outer rubber layer was peeled from the interface between the outer rubber layer and the wire at a peeling rate of 50 mm / min. It peeled and the adhesive force (N / 25mm) which is a magnitude | size (N) per unit width (25mm) required for peeling was measured. Moreover, the wire was peeled off from the rubber sheet, and the surface state of the peeled wire was visually observed. Evaluation with rubber was carried out by calculating the ratio of the wire with rubber attached to the wire surface to the total number of wires attached to the unvulcanized rubber sheet. The numerical values of adhesive strength (N / 25 mm) and with rubber (%) are average values measured four times.

As can be seen from Table 2, with respect to the diene-based polymer, and an amount of sulfur, the rubber composition of Example 1 containing a predetermined amount of the rosin ester, contact adhesive force and with rubber was good. On the other hand, when it did not contain rosin (Comparative Example 1) and when it contained rosins other than the rosin ester (Comparative Example 2-9), the adhesive strength and rubber attachment were significantly reduced. This result is considered to be because, when the rosin ester is not contained, the effect of improving the adhesive force based on the hydrolysis of the ester at the time of heat vulcanization was not exhibited.

DESCRIPTION OF SYMBOLS 1 Hose 11 Internal rubber layer 12 Reinforcement layer 13 External rubber layer 100 Unwinder 101 Mandrel 102 1st extruder 103 Hose 104 Winding unwinding machine 105 Braiding machine 106 Hose 107 Unwinding unwinding machine 108 2nd extruder 109 Hose Main body 110 Winder 111 Vulcanization device 112 Hose 113 Lapping device 114 Unwrapping device 115 Hose 116 Hose 117 Mandrel extraction device 118 Hose 119 Nylon cloth 120 Hot air

Claims (8)

100 parts by mass of a sulfur vulcanizable diene polymer,
0.5 parts by mass or more and 1.5 parts by mass or less of sulfur;
Containing 0.1 to 20 parts by mass of rosin ester,
Ri 0.99 ° C. der than the softening point of 105 ° C. or more of the rosin ester,
The diene polymer has a chloroprene rubber content of 40% by mass or more and 100% by mass or less, and a styrene butadiene rubber content of 0% by mass or more and 60% by mass or less. Composition. The rubber composition according to claim 1, wherein the acid value of the rosin ester is 50 or less. A rubber composition metal laminate comprising: a reinforcing layer having a metal surface; and a rubber layer provided on the reinforcing layer and including the rubber composition according to claim 1. . The rubber composition metal laminate according to claim 3 , wherein the metal surface is brass-plated. The rubber composition metal laminate according to claim 3 or 4 , wherein the reinforcing layer has a braided structure in which wires are knitted and / or a spiral structure. A vulcanized rubber product, wherein the rubber layer of the rubber composition metal laminate according to any one of claims 3 to 5 is vulcanized and bonded to the reinforcing layer. The vulcanized rubber product according to claim 6 which is a hose. The vulcanized rubber product according to claim 7 , wherein the hose is vulcanized by a hot air vulcanization method.

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