WO2016199386A1 - Composition de caoutchouc pour tuyau souple et tuyau souple - Google Patents

Composition de caoutchouc pour tuyau souple et tuyau souple Download PDF

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WO2016199386A1
WO2016199386A1 PCT/JP2016/002698 JP2016002698W WO2016199386A1 WO 2016199386 A1 WO2016199386 A1 WO 2016199386A1 JP 2016002698 W JP2016002698 W JP 2016002698W WO 2016199386 A1 WO2016199386 A1 WO 2016199386A1
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Prior art keywords
rubber
mass
parts
hose
rubber composition
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PCT/JP2016/002698
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English (en)
Japanese (ja)
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常西　洋平
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株式会社ブリヂストン
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Publication of WO2016199386A1 publication Critical patent/WO2016199386A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a rubber composition for hoses and a hose.
  • chlorinated polymers from which vulcanized rubbers used for automobile rubber members, hoses, rubber molds and vibration-proof rubbers, such as chloroprene rubber are heat resistant without impairing mechanical properties, compression set and elongation fatigue properties. It has been studied to further improve (see, for example, Patent Document 2).
  • Patent Document 2 when a large amount of chloroprene rubber having a crystal structure and having a highly reactive chemical structure is added, the self-reactive property is high, so that unvulcanized rubber is easily burnt, which may be a factor in inhibiting productivity.
  • manufacturing defects such as short appearance and poor appearance due to scorching of rubber are likely to occur due to poor standing stability.
  • JP 2010-121006 A International Publication No. 2009/035109
  • the rubber composition for a hose of the present invention includes a rubber component and a chlorine-based flame retardant, and includes less than 70 parts by mass of chloroprene rubber in 100 parts by mass of the rubber component, with respect to 100 parts by mass of the rubber component.
  • the chlorine-based flame retardant is blended in an amount of 5 parts by mass or more.
  • the present invention it is possible to provide a rubber composition for a hose that can achieve both flame retardancy as a vulcanized rubber and standing stability as an unvulcanized rubber. Moreover, according to this invention, the hose which made the flame retardance and the standing stability compatible can be provided.
  • FIG. 1 is a perspective view showing an example of a laminated structure of a hose according to an embodiment of the present invention using the rubber composition for a hose according to an embodiment of the present invention.
  • the rubber composition for hoses of the present invention contains at least a rubber component and a chlorine-based flame retardant, and further contains carbon black, an antimony compound, silica, a plasticizer, and other components as necessary.
  • the rubber composition for a hose of the present invention preferably further contains carbon black. According to this structure, the more outstanding flame retardance and reinforcement
  • the rubber composition for a hose of the present invention preferably further contains an antimony compound, particularly an antimony trioxide compound. According to these configurations, excellent flame retardancy can be stabilized.
  • the rubber component includes at least chloroprene rubber (CR), and further includes styrene-butadiene rubber (SBR), butadiene rubber (BR), and other polymers as necessary.
  • CR chloroprene rubber
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • the rubber composition for a hose of the present invention preferably further contains at least one of styrene-butadiene rubber and butadiene rubber as the rubber component. According to this structure, it can prevent that the abrasion resistance of the rubber composition for hoses falls, or processability (dimensional stability of extrusion, extrusion skin characteristic) can be improved.
  • the chloroprene rubber (CR) is a homopolymer of a chloroprene monomer (chloroprene polymer) or a mixture of a chloroprene monomer and one or more other monomers copolymerizable therewith (hereinafter referred to as a chloroprene series).
  • a copolymer obtained by polymerizing a monomer hereinafter referred to as a monomer
  • a chloroprene copolymer A copolymer obtained by polymerizing a monomer (hereinafter referred to as a monomer) (hereinafter referred to as a chloroprene copolymer).
  • the 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.
  • the sulfur-modified type is inferior in heat resistance of the polymer itself as compared to the mercaptan-modified type and the xanthogen-modified type. Therefore, when more heat resistance is required, the mercaptan-modified type or the xanthogen-modified type is used. It is preferable to use it.
  • the mercaptan-modified type uses alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and octyl mercaptan as molecular weight regulators.
  • the xanthogen-modified type uses an alkyl xanthogen compound as a molecular weight regulator.
  • the alkyl xanthogen compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, and diisobutyl xanthogen disulfide. These may be used individually by 1 type and may use 2 or more types together.
  • the amount of the alkylxanthogen compound used is not particularly limited as long as the molecular weight (or Mooney viscosity) of the chloroprene rubber is appropriate, and the purpose (the structure of the alkyl group and the target molecular weight) is not particularly limited.
  • the amount of chloroprene monomer or chloroprene monomer it is preferably 0.05 to 5.0 parts by weight, more preferably 0.3 to 1.0 parts by weight. preferable.
  • the content of the chloroprene rubber is not particularly limited as long as it is less than 70 parts by mass in 100 parts by mass of the rubber component, and can be appropriately selected according to the purpose. More preferred is ⁇ 65 parts by mass, and particularly preferred is 50 to 60 parts by mass. If the content of the chlorine-based polymer is 70 parts by mass or more in 100 parts by mass of the rubber component, the standing stability cannot be ensured. On the other hand, when the content of the chlorinated polymer is within the above preferred range, it is advantageous in terms of flame retardancy, oil resistance, and weather resistance, and within the more preferred range or within the particularly preferred range. If present, it is advantageous in terms of the balance of flame retardancy, storage stability, oil resistance, and weather resistance.
  • SBR Styrene-Butadiene Rubber
  • SBR Styrene-butadiene rubber
  • a copolymer obtained by polymerizing a mixture with one or more other monomers (hereinafter referred to as a styrene-butadiene monomer).
  • SBR styrene-butadiene rubber
  • the monomer copolymerizable with the styrene monomer and butadiene monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • 2-methyl-1,3-butadiene, 2 Conjugated diene monomers having 5 to 8 carbon atoms such as 1,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene; p-methylstyrene, ⁇ -methylstyrene, vinylnaphthalene, etc.
  • Aromatic vinyl monomer and the like. These may be used individually by 1 type and may use 2 or more types together.
  • SBR styrene-styrene content of butadiene rubber
  • SBR styrene-butadiene rubber
  • SBR styrene-butadiene rubber
  • the styrene content of the styrene-butadiene rubber (SBR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 to 45% by mass, more preferably 20 to 35% by mass.
  • SBR styrene content of the styrene-butadiene rubber
  • SBR styrene-butadiene rubber
  • the styrene content of the styrene-butadiene rubber (SBR) is within the more preferable range, it is more advantageous in terms of workability and wear resistance.
  • SBR -Styrene-butadiene rubber
  • SBR styrene-butadiene rubber
  • the content of the styrene-butadiene rubber (SBR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 40 parts by mass in 100 parts by mass of the rubber component.
  • the content of the styrene-butadiene rubber (SBR) is within the above preferred range, it is advantageous in terms of flame retardancy, wear resistance, and processability (extruded dimensional stability, extruded skin characteristics).
  • the butadiene rubber (BR) is a homopolymer of a butadiene monomer (butadiene polymer), or a mixture of a butadiene monomer and one or more other monomers copolymerizable therewith (hereinafter referred to as a butadiene type).
  • a copolymer obtained by polymerizing a monomer hereinafter referred to as a butadiene copolymer.
  • the butadiene rubber (BR) may be end-modified. Abrasion resistance can be improved by mix
  • BR butadiene rubber
  • the amount of cis-1,4 bonds in the butadiene rubber (BR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 93% or more, and 95% or more. Is particularly preferred. If the amount of cis-1,4 bonds is less than 90% and is unmodified, wear resistance may not be sufficiently improved. On the other hand, even if the amount of cis-1,4 bonds is within the more preferred range or less than 90%, terminal-modified BR is advantageous in terms of wear resistance, and is within the particularly preferred range. Further advantageous.
  • the amount of cis-1,4 bond can be measured using 1 H-NMR, 13 C-NMR, FT-IR, or the like.
  • BR butadiene rubber
  • the content of the butadiene rubber (BR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 40 parts by mass in 100 parts by mass of the rubber component. When the content of the butadiene rubber (BR) is within the preferable range, it is further advantageous in terms of flame retardancy and wear resistance.
  • ⁇ other polymers >> there is no restriction
  • the chlorine-based flame retardant is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a chlorine-based aliphatic compound such as chlorinated paraffin
  • a chlorine-based phosphorus compound such as a chlorine-based phosphate ester compound And composite flame retardants.
  • chlorinated aliphatic compounds are preferred, and chlorinated paraffins are more preferred.
  • the chlorination rate of the chlorinated paraffin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 to 70%. When the chlorination rate of the chlorinated paraffin is within the preferable range, it is advantageous in terms of flame retardancy. There is no restriction
  • Specific examples of the chlorinated phosphate ester compound are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trischloropropyl phosphate, a condensate of trischloropropyl phosphate and dialkylene glycol, and the like. Is mentioned.
  • the chlorinated flame retardant is preferably a chlorinated aliphatic compound, and the chlorinated aliphatic compound is more preferably chlorinated paraffin. According to these structures, a flame retardance can be ensured more reliably.
  • the amount of the chlorine-based flame retardant is not particularly limited as long as it is 5 parts by mass or more with respect to 100 parts by mass of the rubber component, and can be appropriately selected according to the purpose. Is more preferably 20 parts by mass or more, and particularly preferably 20 to 30 parts by mass. Flame retardance will fall that the compounding quantity of the said chlorine-type flame retardant is less than 5 mass parts with respect to 100 mass parts of said rubber components. On the other hand, when it is within the above preferable range or the above particularly preferable range, it is advantageous in terms of flame retardancy and storage stability. In addition, when a chlorinated flame retardant is chlorinated paraffin, it is desirable to set it as 50 mass parts or less from a viewpoint of abrasion resistance or breaking strength.
  • the rubber composition for hose of the present invention 30 parts by mass or more of the chloroprene rubber is contained in 100 parts by mass of the rubber component, and the chlorine-based flame retardant is 20 parts by mass with respect to 100 parts by mass of the rubber component. It is preferable to be blended as described above. According to this structure, flame retardance can be ensured more reliably.
  • the chlorinated paraffin is preferably blended with 100 parts by mass of the rubber component, and the chlorinated paraffin has a chlorination rate of 40 to 70. % Is more preferable. According to these structures, both flame retardancy and storage stability can be achieved more reliably.
  • Carbon black By adding the carbon black to the rubber component, it is possible to ensure reinforcement and flame retardancy.
  • the FEF class (iodine adsorption 40 to 60 mg / g (g / kg), DBP oil absorption 100 to 130 mL / 100 g (100 ⁇ 10 ⁇ 5 m 3 / kg to 130 ⁇ 10 ⁇ 5 m 3 / kg) is desirable.
  • the iodine adsorption amount of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 to 160 mg / g, and more preferably 40 to 60 mg / g.
  • the iodine adsorption amount of the carbon black is within the above preferable range, it is advantageous in terms of the balance of wear resistance and workability, and when it is within the above preferable range, it is further advantageous.
  • the DBP oil absorption amount of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 30 to 150 mL / 100 g, more preferably 100 to 130 mL / 100 g.
  • the DBP oil absorption amount of the carbon black is within the above preferable range, it is advantageous in terms of the balance between wear resistance and workability, and when it is within the above preferable range, it is further advantageous.
  • the carbon black preferably has an iodine adsorption of 20 to 160 mg / g, a DBP oil absorption of 30 to 150 mL / 100 g, an iodine adsorption of 40 to 60 mg / g, and a DBP oil absorption of 100 to 100 mg / g. More preferably, it is 130 mL / 100 g. If the iodine adsorption amount and DBP oil absorption amount of the carbon black are within the above preferred ranges, it is advantageous in terms of the balance between wear resistance and processability, and more advantageously within the above preferred ranges.
  • the blending amount of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the rubber component. It is advantageous in terms of flame retardancy and workability when the blending amount of the carbon black is within the preferred range with respect to 100 parts by mass of the rubber component.
  • Antimony compound By adding the antimony compound to the rubber component, flame retardancy can be further stabilized.
  • antimony trioxide for example, antimony trioxide, antimony pentoxide, sodium antimonate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, antimony trioxide is preferable in terms of stabilizing excellent flame retardancy.
  • the nitrogen adsorption specific surface area of the silica is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 70 ⁇ 300m 2 / g, more preferably 100 ⁇ 280m 2 / g 150 to 250 m 2 / g is particularly preferable.
  • the nitrogen adsorption specific surface area (N 2 SA) of the silica is 70 m 2 / g or more, the effect of improving flame retardancy and wear resistance can be sufficiently obtained, and it is 300 m 2 / g or less. The effect of improving dispersibility and workability can be sufficiently obtained.
  • the nitrogen adsorption specific surface area (N 2 SA) of the silica is within the above preferable range, it is advantageous in terms of the balance of flame retardancy, wear resistance, dispersibility, and workability, and the above is particularly preferable. Within the range, it is further advantageous.
  • the compounding amount of the silica is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 to 25 parts by mass, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • the amount of silica is 5 parts by mass or more, flame retardancy can be improved (especially afterglow disappearance time is shortened), and when it is 25 parts by mass or less, it is prevented from becoming too hard. can do.
  • the blending amount of the silica is within the above preferable range, the blending ratio of each component of the present application is more advantageous in terms of flame retardancy and workability (extruded dimensional stability, extruded skin characteristics). is there.
  • the rubber composition for a hose of the present invention it is preferable that 5 to 25 parts by mass of silica is further blended with 100 parts by mass of the rubber component. According to this configuration, flame retardancy can be improved (particularly, the afterglow disappearance time can be shortened), and workability (extruded dimensional stability, extruded skin characteristics) can be improved.
  • plasticizer By adding the plasticizer to the rubber composition for a hose, initial elongation (flexibility, and consequently crack resistance) can be improved.
  • plasticizer there is no restriction
  • the mixing ratio of the spindle oil and aroma oil mixture is not particularly limited and may be appropriately selected depending on the intended purpose. preferable.
  • the mixing ratio is 1/2 or more, an effect of preventing an increase in adhesion during processing can be sufficiently obtained, and when it is 1/1 or less, the flame retardancy is prevented from being lowered. Can do.
  • the blending amount of the plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 parts by mass or less, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the rubber component. 10 to 15 parts by mass are preferable. Even when the plasticizer is blended, the flame retardancy is prevented from being lowered when the blending amount of the plasticizer is 20 parts by mass or less with respect to 100 parts by mass of the rubber component. it can. On the other hand, when the blending amount of the plasticizer is within the more preferable range, it is advantageous in terms of balance between flame retardancy, initial elongation (flexibility, and crack resistance) and workability, and the above is particularly preferable. Within the range, it is further advantageous.
  • the rubber composition for hose of the present invention it is preferable that 20 parts by mass or less of a plasticizer is further blended with 100 parts by mass of the rubber component. According to this configuration, flexibility can be further improved while ensuring flame retardancy.
  • inorganic fillers such as talc, clay and calcium carbonate; vulcanizing agents such as peroxide vulcanizing agents; vulcanization accelerators; zinc oxide (zinc white), Vulcanization accelerators such as stearic acid; vulcanization retarder; anti-aging agent; wax; anti-scorch agent; softener; silane coupling agent, organic acid metal salt (organic acid cobalt etc.), resorcin, hexamethylenetetramine,
  • An object of the present invention is a compounding agent usually used in the rubber industry, such as an adhesion assistant such as melamine resin; a metal compound such as magnesium oxide, calcium oxide, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide; Can be appropriately selected and blended within a range that does not harm the above.
  • these compounding agents commercially available products can be suitably used.
  • the above rubber composition is produced by blending the above-mentioned various compounding agents appropriately selected as necessary with the essential components composed of a rubber component and a chlorine-based flame retardant, kneading, heating, extruding, and the like. can do.
  • the hose of the present invention has at least a rubber layer, and further includes layers other than the rubber layer and other members as necessary.
  • the hose of the present invention has a rubber layer using the rubber composition for a hose of the present invention. According to the hose of the present invention, both flame retardancy and storage stability can be achieved.
  • the rubber layer is composed of the rubber composition for hoses of the present invention.
  • middle rubber layer which does not form the inner and outer surface of a hose, and / or the outer surface of a hose is formed.
  • the outer surface rubber layer (outer rubber layer) and the like are particularly preferable.
  • the outer surface rubber layer is preferably the rubber layer.
  • the thickness of the outer rubber layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.3 to 3.5 mm, more preferably 0.7 to 3.2 mm, and 1.0 Particularly preferred is ⁇ 3.0 mm. If the thickness of the outer rubber layer is 0.3 mm or more, it can be prevented from wearing and reaching an early life, and if it is 3.5 mm or less, the flame retardancy decreases due to an increase in the amount of combustion components. This can be prevented, or it can be prevented that the hose is inferior in terms of flexibility, weight reduction, and space saving. On the other hand, if the thickness of the outer rubber layer is within the more preferable range, it is more advantageous in terms of flame retardancy and wear life, and it is more advantageous if it is within the particularly preferable range.
  • a hose 1 is a hydraulic hose, an inner rubber layer 10, reinforcing layers 12, 14, 16, 18 having brass plating wires, intermediate rubber layers 11, 13, 15, 17, and outer rubber layers. 19.
  • the rubber composition for a hose of the present invention is suitable for use in at least the outer rubber layer 19, and is used for all or a part of the intermediate rubber layers 11, 13, 15, 17 and the outer rubber layer 19. You can also.
  • the hose has an inner rubber layer 10 from the inner side, four reinforcing layers 12, 14, 16, 18 and intermediate rubber layers 11, 13, 15, 17, and an outer rubber layer 19, respectively.
  • the present invention is not limited to this.
  • a three-layer structure in which an inner rubber layer, a reinforcing layer, and an outer rubber layer are sequentially laminated may be used. It can be appropriately selected depending on the case.
  • it is not necessary for all the reinforcing layers to be formed of a brass plating wire, and a reinforcing layer partially formed of organic fibers can also be used.
  • a hose in which a resin layer such as ultra high molecular weight polyethylene is disposed on the outermost layer to improve wear resistance may be used.
  • a method for producing the hose of the present invention for example, as follows, an inner tube extrusion step, a braiding step, a jacket extrusion step, a resin mold coating step, a vulcanization step, and a resin mold peeling step And a mandrel extraction step, and a method including other steps appropriately selected as necessary.
  • the hose having the structure shown in FIG. 1 will be described as an example.
  • a rubber composition for the inner rubber layer 10 is extruded on the outer side of a core body (mandrel) having a diameter approximately equal to the inner diameter of the hose to cover the mandrel. Then, the inner rubber layer 10 is formed (inner tube extrusion step).
  • the layer formed with an organic fiber can also be introduce
  • a predetermined number of brass plating wires are knitted outside the inner rubber layer 10 formed by the inner tube extrusion step to form a reinforcing layer 12 (knitting step), and the hose of the present invention is formed inside the reinforcing layer 12.
  • the intermediate rubber layer 11 is formed by inserting and forming a sheet of the rubber composition.
  • the reinforcing layers 14, 16, 18 and the intermediate rubber layers 13, 15, 17 are sequentially laminated to extrude the outer surface rubber layer 19 made of the rubber composition for hose of the present invention (outer extrusion process) ).
  • the outer surface of the outer rubber layer 19 formed in the outer shell extrusion step is appropriately coated with a suitable resin (resin mold coating step), and vulcanized under predetermined conditions (vulcanization step). After vulcanization, the coating resin is peeled off (resin mold peeling step), and the mandrel is removed (mandrel extraction step), whereby intermediate rubber layers 11, 13, 15 are interposed between the inner rubber layer 10 and the outer rubber layer 19. 17 and the reinforcing layer 12, 14, 16, 18 are obtained.
  • the polymer and rubber composition described below were prepared.
  • the evaluation method of a rubber composition is shown below.
  • the unit of the values described as the blending amounts in Tables 1 to 6 is parts by mass.
  • the rubber compositions of Examples and Comparative Examples have (i) 5 parts by mass of zinc oxide, (ii) 4 parts by mass of magnesium oxide, and (iii) with respect to 100 parts by mass of the rubber component.
  • Wax (OZOACE0017, Nippon Seiwa Co., Ltd.) 2 parts by mass, (iv) Anti-aging agent (ANTIGENE 6C, Sumitomo Chemical Co., Ltd.) 3 parts by mass, (v) Cobalt stearate 2 parts by mass, (vi) 1 part by mass of sulfur and (vii) 2 parts by mass of vulcanization accelerator (NS) are further contained.
  • ANTIGENE 6C Sumitomo Chemical Co., Ltd.
  • Viscosity increase rate [ ⁇ ML 1 + 4 (AGED) ⁇ ⁇ ⁇ ML 1 + 4 (ORI) ⁇ ] / ⁇ ML 1 + 4 (ORI) ⁇
  • Tables 1 to 6 show the evaluation results based on the obtained measurement results. The evaluation criteria are as follows. ⁇ : 50% or less ⁇ : More than 50% 100% or less ⁇ : More than 100%
  • the rubber composition for a hose of the present invention can be suitably used, for example, for an intermediate rubber layer and / or an outer rubber layer of a hydraulic hose of a hydraulic excavator used in a coal mine or a mine.
  • hose 10: inner rubber layer, 11, 13, 15, 17: intermediate rubber layer, 12, 14, 16, 18: reinforcing layer, 19: outer rubber layer

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

Abstract

L'invention concerne une composition de caoutchouc qui est destinée à un tuyau souple et qui permet d'obtenir à la fois les propriétés retardatrices de flamme d'un caoutchouc vulcanisé et la stabilité de conservation d'un caoutchouc non vulcanisé. L'invention concerne également un tuyau souple. Cette composition de caoutchouc pour tuyau souple contient un constituant de caoutchouc et un retardateur de flamme à base de chlore, et est caractérisée en ce qu'elle comprend moins de 70 parties en masse de caoutchouc de chloroprène dans 100 parties en masse du constituant de caoutchouc et en ce qu'elle comprend 5 parties en masse ou plus du retardateur de flamme à base de chlore pour 100 parties en masse du constituant de caoutchouc.
PCT/JP2016/002698 2015-06-09 2016-06-03 Composition de caoutchouc pour tuyau souple et tuyau souple WO2016199386A1 (fr)

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JP2015117000A JP2017002173A (ja) 2015-06-09 2015-06-09 ホース用ゴム組成物及びホース
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106704731A (zh) * 2016-12-14 2017-05-24 安徽德耐孚汽车减震科技技术有限公司 一种耐油橡胶管及其制造工艺
US10590253B2 (en) 2015-07-13 2020-03-17 The Yokohama Rubber Co., Ltd. Rubber composition for flame-retardant hose, and flame-retardant hose

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JP2023023119A (ja) * 2021-08-04 2023-02-16 横浜ゴム株式会社 ホース用ゴム組成物及びホース

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US10590253B2 (en) 2015-07-13 2020-03-17 The Yokohama Rubber Co., Ltd. Rubber composition for flame-retardant hose, and flame-retardant hose
CN106704731A (zh) * 2016-12-14 2017-05-24 安徽德耐孚汽车减震科技技术有限公司 一种耐油橡胶管及其制造工艺

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