JP6467802B2 - Rubber composition metal laminate for hose and vulcanized rubber product - Google Patents

Description

  The present invention relates to a rubber composition for a hose, a rubber composition metal laminate for a hose, and a vulcanized rubber product, and more specifically, a rubber composition for a hose containing a rosin, a rubber composition metal laminate for a hose, and It relates to vulcanized rubber products.

  Conventionally, a rubber composition for bonding a brass plating wire for 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 has been proposed (for example, see Patent Document 1). In this rubber composition, adhesiveness with a brass plating wire and heat resistance are improved by containing a predetermined amount of rosin acid as an organic acid.

JP 2012-051978 A

  By the way, these hydraulic hoses and high pressure hoses such as hoses can be produced by a steam vulcanization system in which the rubber composition for the hose is heated and vulcanized with steam, or by heating the rubber composition for the hose in an oven. There is a hot air vulcanization method (oven vulcanization method).

  However, in the conventional rubber composition, when the rubber composition for hoses is vulcanized by the steam vulcanization method, sufficient adhesiveness may not always be obtained. For this reason, even when vulcanized by a steam vulcanization method, a rubber composition for a hose is desired that can provide a rubber layer having excellent adhesion to the reinforcing layer.

  The present invention provides a rubber composition for a hose, a rubber composition metal laminate for a hose, and a vulcanized rubber product that are excellent in adhesion to a reinforcing layer even when vulcanized by a steam vulcanization method. For the purpose.

  The rubber composition for a hose of the present invention comprises 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 or more of rosins. And 20 parts by mass or less.

  In the rubber composition for a hose 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. The following is preferable.

  In the rubber composition for a hose of the present invention, the rosins preferably have a softening point of 50 ° C. or higher and 150 ° C. or lower.

  In the rubber composition for a hose of the present invention, the acid value of the rosins is preferably 50 or more.

  The rubber composition metal laminate for a hose 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 for a hose.

  In the rubber composition metal laminate for a hose of the present invention, the metal surface is preferably subjected to brass plating.

  In the rubber composition metal laminate for a hose 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 for a hose 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 steam vulcanizer.

  According to the present invention, a rubber composition for a hose, a rubber composition metal laminate for a hose, and a vulcanized rubber product excellent in adhesiveness to a reinforcing layer even when vulcanized by a steam vulcanization method. realizable.

FIG. 1 is a schematic partially broken perspective view showing an example of a hose according to an embodiment of the present invention. Drawing 2 is an explanatory view of the manufacturing process of a hose using the rubber composition for hoses concerning an embodiment of the invention. FIG. 3 is a partial cross-sectional view showing an example of a layer structure around a mandrel that is put into a vulcanizing apparatus in a hose manufacturing process using the hose 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 for a hose 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% of rosin. From 20 parts by mass to 20 parts by mass.

  According to this rubber composition for hoses, since a predetermined amount of rosins is contained in the diene polymer capable of sulfur vulcanization, the rubber composition is imparted with appropriate tackiness by the rosins, and steam vulcanization is performed. The reaction between the metal surface of the reinforcing layer and sulfur during vulcanization in the sulfur system is promoted, and the adhesive strength between the rubber composition for a hose after vulcanization and the metal surface of the reinforcing layer is improved. Hereinafter, various components of the rubber composition for a hose 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 a hose required for a rubber composition for a hose 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 for hoses and adhesion to the metal surface of the reinforcing layer, the content of chloroprene rubber (CR) is 40% by mass or more and 100% by mass or less, It is preferable to use a styrene butadiene rubber (SBR) having a 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 for a hose from the viewpoint of good rubber mixing processability and a good rubber appearance.

<Rosin>
The rubber composition for hoses according to the present embodiment contains rosins. By containing this rosin, moderate tackiness is imparted to the rubber composition at the time of vulcanization under steam vulcanization conditions, so even when vulcanized by the steam vulcanization method, Adhesion is improved.

  Examples of rosins include unmodified rosin (natural rosin) such as gum rosin, wood rosin, and tall rosin, and unmodified rosin such as unsaturated carboxylic acid such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid and acrylic acid. Acid-modified unsaturated carboxylic acid-modified rosin (eg maleated rosin and acrylated rosin), hydrogenated rosin hydrogenated unmodified rosin (hydrogenated rosin), polymerized rosin polymerized unmodified rosin, unmodified Examples thereof include a disproportionated rosin obtained by disproportionating rosin, a phenol-modified rosin obtained by modifying an unmodified rosin with a phenol, and a formylated rosin obtained by subjecting an unmodified rosin to formalin treatment (rosin derivative). These modified rosins include rosin-containing diols (rosin diols) having two rosin skeletons and two hydroxyl groups in the molecule. These rosins may be used alone or in combination of two or more.

  As the rosins, rosins other than rosin acid are preferably used. As rosins, among rosins and rosin derivatives, gum rosin, wood rosin, tall rosin, acrylic rosin, hydrogenated rosin, polymerized rosin, disproportionated rosin, phenol-modified rosin, formylated rosin and rosin diol It is more preferable to use at least one selected, and among rosin and rosin derivatives, at least one selected from the group consisting of gum rosin, wood rosin, tall rosin, acrylated rosin, hydrogenated rosin, polymerized rosin and disproportionated rosin. More preferably, it is used.

  Moreover, a commercial item can also be used as rosins. Commercially available rosins include gum rosin (trade names “Gum rosin WW”, “Gum rosin X”, manufactured by Harima Kasei Co., Ltd.), tall rosin (trade names “Hartol R-WW”, manufactured by Harima Chemical Co., Ltd.), acrylated rosin (commodities) Name "Harimak (registered trademark) T-80", manufactured by Harima Chemicals Co., Ltd.), hydrogenated rosin (trade name "Haritac (registered trademark) F", manufactured by Harima Chemicals Co., Ltd., product name "High Veil (registered trademark)", Arakawa Chemical Industrial Co., Ltd.), Polymerized Rosin (trade name “Aradaim (registered trademark) R-95”, manufactured by Arakawa Chemical Industry Co., Ltd.), Disproportionated Rosin (trade name “Longis (registered trademark) R”, manufactured by Arakawa Chemical Industries, Ltd.) Etc.

  The rosins are preferably those having a softening point of 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of obtaining a rubber composition for a hose excellent in adhesion to the metal surface of the reinforcing layer. Those having a temperature of not lower than ° C 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 in accordance with JIS K 6220-1: 2001.

  As the rosins, those having an acid value of 50 or more are preferable, those having an acid value of 75 or more are more preferable, those having an acid value of 100 or more are more preferable, those having 250 or less are preferable, and those having 225 or less are more preferable. What is 200 or less is still more preferable. Considering the above, the acid value of rosins is preferably 50 or more and 250 or less, more preferably 75 or more and 225 or less, and still more preferably 100 or more and 200 or less. In the present embodiment, the acid value is a value measured by a neutralization titration method or a potential titration method in accordance with JIS K 0070: 1992.

  The blending amount of rosins 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 for hoses excellent in adhesion to the metal surface of the reinforcing layer. 0.5 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 more 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. Preferably, 7 parts by mass or less is more preferable. Considering the above, the blending amount of rosins is 0.1 parts by mass or more and 20 parts by mass or less, 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.

<Vulcanizing agent>
The rubber composition for hoses 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. If the sulfur content is 0.5 parts by mass or more and 1.5 parts by mass or less, the hose rubber has excellent heat resistance as well as excellent adhesion between the rubber layer using the hose rubber composition and the reinforcing layer. A composition is obtained. 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.

  In the rubber composition for hoses which concerns on this Embodiment, the vulcanizing agents other than sulfur may be included within the range with the effect of this invention. 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 for hoses 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, and N, N-dicyclohexyl-2-benzothiazolylsulfenamide.

  Examples of the thiourea vulcanization accelerator include ethylenethiourea (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 adhesiveness between the reinforcing layer and the rubber layer containing the rubber composition for hoses. 0.75 mass part or more is more preferable, 1.0 mass part or more is further more preferable, 3.0 mass part or less is preferable, 2.5 mass part or less is more preferable, and 2.0 mass part or less is still more preferable.

[Other additives]
Moreover, the rubber composition for hose can contain another additive as needed in the range with the effect of this invention. 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, N-nitroso-trimethyl-dihydroquinoline Examples thereof include nitroso compounds such as coalescence, 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 for hose>
The rubber composition for a hose according to the present embodiment can be produced by a conventionally known production method. As a method for producing a rubber composition for a hose according to the present embodiment, for example, first, 100 parts by mass of a sulfur-vulcanizable diene polymer, 0.5 to 1.5 parts by mass of sulfur, In addition, 0.1 part by mass or more and 20 parts by mass or less of rosin, 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 for hose]
The rubber composition metal laminate for hose according to the present embodiment is a laminate of the rubber composition for hose 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 for hoses 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 for a hose according to the above embodiment. The inner rubber layer 11 is preferably formed using a rubber composition for hoses 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 wire is wound around the inner rubber layer 11 in a spiral shape. 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 for hose rubber composition of the rubber composition for hose and the reinforcing layer 12 is a rubber that forms the inner rubber layer 11 and the outer rubber layer 13 by crosslinking, that is, vulcanizing in the presence of sulfur. These molecules are 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 for hoses. 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 for a hose is heat-treated 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. Examples of a method for producing a hose include a steam vulcanization method in which a rubber composition metal laminate for a hose is enclosed in a high-pressure vessel and crosslinked in a steam can. Generally, the steam vulcanization method is a batch type treatment.

<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, the manufacturing method of the hose which concerns on this Embodiment is demonstrated. Drawing 2 is an explanatory view of the manufacturing process of a hose using the rubber composition for hoses concerning an embodiment of the invention.

<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. Thereafter, the hose body 109 is enclosed in a high-pressure vessel (not shown) and crosslinked in a steam can to carry out the vulcanization process.

  Next, in step S104, after vulcanization, the mandrel 101 is extracted from the hose body 109 after vulcanization from the winder 110 by the mandrel extraction device 117, and the hose 118 is completed.

  FIG. 3 is a partial cross-sectional view showing an example of the layer structure around the mandrel 101 to be charged into the vulcanizer. As shown in FIG. 3, 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 internal rubber layer 11 and / or the external rubber layer 13 using the rubber composition for a hose according to the above embodiment, the internal rubber layer 11 and / or the external rubber layer 13 and a metal reinforcement are formed. A hose with good adhesion to the layer 12 can be produced.

  In addition, it cannot be overemphasized that the rubber composition for hoses which concerns on the said embodiment can be used conveniently also for manufacture of the rubber product by another conventionally well-known vulcanization system. Examples of other vulcanization methods include press 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.

  Moreover, in this Embodiment, although demonstrated using the hose as a rubber composition metal laminated body for hose and a vulcanized rubber product, this invention is not limited to this, For example, other conveyor belts etc. It can be similarly used in a rubber laminate.

  As described above, according to the rubber composition for a hose according to the present embodiment, the rubber composition is imparted with appropriate adhesiveness by the rosins, so even when vulcanized by the steam vulcanization method A vulcanized rubber product having good adhesion between the rubber layer and the reinforcing layer can be provided. Moreover, even if it is a case where it is used after storing for a long time in a dry state, the rubber composition which forms a rubber product with favorable adhesiveness with a reinforcement layer can be provided. Furthermore, the vulcanized rubber product obtained using this rubber composition can be suitably used for hoses such as hydraulic hoses and high-pressure hoses.

  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.

<1. Preparation of rubber composition for hose>
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 (gum rosin, trade name “Gum rosin WW”, manufactured by Arakawa Chemical Industries) (Rosin ester, trade name “Harimak (registered trademark) R-80”, manufactured by Harima Chemical Co., Ltd.) and 0.75 parts by mass of sulfur ( Hosoi Chemical Co., Ltd.) and 0.75 parts by mass of (vulcanization accelerator A: tetramethylthiuram monosulfide, trade name “SA” "Nseller TS-G" (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.75 parts by mass of vulcanization accelerator B (N, N'-diphenylguanidine, trade name "Soccinol DG", manufactured by Sumitomo Chemical Co., Ltd.) , 45 parts by mass of carbon black A (FEF grade carbon black (trade name “HTC # 100”, manufactured by Nisshin Carbon Co., Ltd.)) and 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, 10 parts by mass of aroma oil (trade name" A-OMIX ", manufactured by Sankyo Oil Chemical Co., Ltd.), and 2 parts by mass of fatty acid ester (dioctyl) Adipate, trade name “DIACIZER DOA”, manufactured by Mitsubishi Kasei Vinyl Co., Ltd., 2 parts by weight of anti-aging agent (trade name “Ozone Non 6C”, manufactured by Seiko Chemical Co., Ltd.), and 1.6 parts by weight Paraffin wax A, 2.4 parts by mass of paraffin wax B, 2 parts by mass of vulcanization retarder, 5 parts by mass of zinc oxide (3 types of zinc oxide, manufactured by Shodo Chemical Co., Ltd.), and 3 parts by mass Was mixed with stearic acid (manufactured by NOF Corporation) and kneaded with a Banbury Kimiser to produce a rubber composition for a hose and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Example 2)
A rubber composition for a hose was prepared and evaluated in the same manner as in Example 1 except that 5 parts by mass of rosin B (gum rosin, trade name “Gum rosin X”, 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.

(Example 3)
A rubber composition for a hose was prepared in the same manner as in Example 1 except that 5 parts by mass of rosin C (Tall rosin, trade name “Hartol R-WW”, manufactured by Harima Kasei Co., Ltd.) was blended in place of rosin A. And evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

Example 4
For hose in the same manner as in Example 1 except that 5 parts by mass of rosin D (acrylic rosin, trade name “Harimak (registered trademark) T-80”, manufactured by Harima Chemical Co., Ltd.) was used instead of rosin A. A rubber composition was prepared and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Example 5)
A rubber composition for a hose in the same manner as in Example 1 except that 5 parts by mass of rosin E (hydrogenated rosin, trade name “Halitak (registered trademark) F”, manufactured by Harima Chemical Co., 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.

(Example 6)
Rubber composition for hose in the same manner as in Example 1 except that 5 parts by mass of rosin F (hydrogenated rosin, trade name “HIVEL (registered trademark)”, 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.

(Example 7)
For hose in the same manner as in Example 1 except that 5 parts by mass of rosin G (polymerized rosin, trade name “Aradaim (registered trademark) R-95”, manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A. A rubber composition was prepared and evaluated. The amount of each component is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

(Example 8)
For hose in the same manner as in Example 1 except that 5 parts by mass of rosin H (disproportionated rosin, trade name “Longis (registered trademark) R”, manufactured by Arakawa Chemical Industries, Ltd.) was blended in place of rosin A A rubber composition was prepared 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 for hoses was prepared and evaluated in the same manner as in 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.

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., non-sulfur 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: Gum rosin, trade name “Gum rosin WW”, manufactured by Arakawa Chemical Industries ・ Rosin B: Gum rosin, trade name “Gum rosin X”, manufactured by Harima Kasei Co., Ltd. ・ Rosin C: Tall rosin, trade name “Hartol R-WW”, Made by Harima Kasei Co., Ltd./Rosin D: Acrylicized rosin, trade name “Harimak (registered trademark) T-80”, produced by Harima Kasei Co., Ltd./Rosin E: hydrogenated rosin, trade name “Halitac (registered trademark) F”, Harima Chemical・ Rosin F: hydrogenated rosin, trade name “High Veil (registered trademark)”, Harima Kasei Co., Ltd. ・ Rosin G: polymerized rosin, trade name “Aradym (registered trademark) R-95”, manufactured by Arakawa Chemical Industries, Ltd. Rosin H: disproportionated rosin, trade name “Longis (registered trademark) R”, manufactured by Arakawa Chemical Industries, Sulfur: manufactured by Hosoi Chemical Co., Ltd., vulcanization accelerator A: tetramethylthiuram monosulfide, quotient 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 Nisshin Carbon Co., Ltd. ・ Carbon black B: ISAF grade carbon black: trade name “Show Black N220”, Showa Cabot Co., Ltd., naphthen oil: trade name “Cosmolex H22 (YR) ) ", Aroma oils manufactured by JX Nippon Mining Energy Co., Ltd .: Trade name" A-OMIX ", Fatty acid ester: Dioctyl adipate, manufactured by Sankyo Oil Chemical Co., Ltd. Trade name “Ozone Non 6C”, Seiko Chemical Co., Ltd., Paraffin Wax A: Trade name “OZOACE-0015A” Nippon Seiwa Co., Ltd., Paraffin Wax B: Trade name “OZOACE-0037”, Nippon Seiwa Co., Ltd., Vulcanization retarder: Trade name “Kyowa Mag 150”, Kyowa Chemical Industry Co., Ltd., zinc oxide: 3 types of zinc oxide, Shodo Chemical 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 for a hose having the composition shown in Table 1 is 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. Brass plating is performed under the following conditions. The adhesion to the wire was evaluated.

(Adhesion evaluation 1: initial adhesion, wire peeling test)
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 is vulcanized in a steam can at 143 ° C. under steam vulcanization conditions for 90 minutes, and then the outer rubber layer is peeled from the interface between the outer rubber layer and the wire at a peeling rate of 50 mm / min. Was peeled, and the adhesive force (N / 25 mm), which is the magnitude (N) per unit width (25 mm) 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.

(Adhesion evaluation 2: after wet heat degradation)
The prepared unvulcanized rubber sheet was placed in a constant temperature and high humidity chamber with a relative humidity of 95% RH at 50 ° C. for 168 hours, then taken out of the high temperature and high humidity chamber, and the wire was peeled off from the rubber sheet within 2 hours. The state of the surface was visually observed.

  As can be seen from Table 2, the rubber composition for a hose according to Example 1-8 containing a predetermined amount of sulfur and a predetermined amount of rosins with respect to the diene polymer is a rosin having any structure. Even when it was used, both had good adhesion and rubber. On the other hand, when no rosin was contained, the adhesive strength and rubber attachment were significantly reduced (Comparative Example 1). This result is considered to be because when the rosins were not contained, the rubber composition was not given tackiness by the rosins during the heat vulcanization, and the effect of improving the adhesive strength 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 Vulcanizing device 117 Mandrel extraction device 118 Hose 119 Nylon cloth

Claims (6)

A reinforcing layer having a metal surface formed by brass plating ;
Provided on the reinforcing layer, Rutotomoni and a rubber layer containing a rubber composition for a hose,
The rubber composition for hose is
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 rosins,
The acid value of the rosins is more than 135 and 150 or less, and
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. Rubber composition metal laminate for use. The rubber composition metal laminate for a hose according to claim 1 , wherein the reinforcing layer has a braided structure in which wires are knitted and / or a spiral structure. The rubber composition metal laminate for hoses according to claim 1 or 2, wherein a softening point of the rosins is 50 ° C or higher and 150 ° C or lower. The vulcanized rubber product, wherein the rubber layer of the rubber composition metal laminate for a hose according to any one of claims 1 to 3 is vulcanized and bonded to the reinforcing layer. . The vulcanized rubber product according to claim 4 which is a hose. The vulcanized rubber product according to claim 5 , wherein the hose is vulcanized by a steam vulcanizer.

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