WO2014126015A1 - ホース用ゴム組成物及びホース - Google Patents

ホース用ゴム組成物及びホース Download PDF

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WO2014126015A1
WO2014126015A1 PCT/JP2014/052890 JP2014052890W WO2014126015A1 WO 2014126015 A1 WO2014126015 A1 WO 2014126015A1 JP 2014052890 W JP2014052890 W JP 2014052890W WO 2014126015 A1 WO2014126015 A1 WO 2014126015A1
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Prior art keywords
rubber
mass
parts
hose
rubber composition
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English (en)
French (fr)
Japanese (ja)
Inventor
篤 川合
常西　洋平
鈴木　貴彦
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Bridgestone Corp
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Bridgestone Corp
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Priority to AU2014217187A priority Critical patent/AU2014217187B2/en
Priority to CN201480008795.9A priority patent/CN104995249B/zh
Priority to US14/766,897 priority patent/US20150368448A1/en
Publication of WO2014126015A1 publication Critical patent/WO2014126015A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C08L9/02—Copolymers with acrylonitrile
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/40—Thiurams, i.e. compounds containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • 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
    • 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
    • F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the present invention relates to a rubber composition excellent in adhesiveness with a brass plating wire, and particularly suitable for use as an inner tube rubber of a hydraulic hose, and a hose manufactured using the rubber composition.
  • NBR acrylonitrile butadiene rubber
  • brass plating wire is generally used for the reinforcing layer laminated on the outer side of the inner tube rubber. It is used for.
  • the NBR and the brass plating wire do not necessarily have sufficient adhesiveness, and may be peeled off at the interface due to bending, vibration or the like during use, which may cause early product damage.
  • Patent Document 1 JP-A-58-72436
  • Patent Document 2 JP-A-59-162648
  • the method using these auxiliaries causes inconveniences such as cost increase and workability deterioration.
  • rubber hardness may be increased and fatigue resistance may be lowered.
  • unvulcanized and vulcanized compounds may be used depending on the functional group of the modified polymer. The surface tackiness of the rubber is excessively increased, which may adversely affect workability and the appearance of the product.
  • TMTD tetramethylthiuram disulfide
  • TMTM tetramethylthiuram monosulfide
  • TETD tetraethylthiuram disulfide
  • TBTD tetrabutylthiuram disulfide
  • the thiuram compounds are materials with high environmental risks because of concern about the generation of harmful substances nitrosamines and mutagenicity.
  • a hose in which the inner tube rubber is formed of a rubber composition having improved adhesion using a thiuram compound is likely to cause bulging of the inner tube rubber (rubber bulging of the bracket crimping portion). Yes.
  • the present invention has been made in view of the above circumstances, and is a rubber composition, particularly an inner tube of a hydraulic hose, which can obtain good adhesiveness with a brass-plated wire and which can also solve environmental risks and bulge problems. It aims at providing the rubber composition which can be used suitably as rubber
  • the present inventors can generate nitrosamine, which is a harmful substance, by using a thiuram compound represented by the following general formula (1) as a vulcanization accelerator. It has been found that it is possible to prevent as much as possible, and that sufficient adhesiveness with a brass-plated wire can be obtained by optimizing the blending amount and using an appropriate amount of a phenol resin. In addition, as a result of further investigation, it was found that by adding an appropriate amount of bismaleimide as a co-crosslinking agent, it is possible to prevent the occurrence of bulges when making hose inner tube rubber as much as possible. The present invention has been completed by examining the appropriate amount of a compounding agent such as zinc white.
  • a compounding agent such as zinc white.
  • R is an alkyl group or aryl group having 6 or more carbon atoms, and may be different from each other or two or more may be the same.
  • the present invention provides the following rubber composition for hoses and a hose using the rubber composition.
  • acrylonitrile butadiene rubber NBR
  • a rubber composition for a hose comprising 1 to 5 parts by mass of a thiuram compound represented by the general formula (1).
  • the rubber composition of the present invention uses a specific thiuram compound represented by the above formula (1) as a vulcanization accelerator, optimizes the addition amount thereof, and adds this and a phenol resin to improve various oil resistance and the like. It can be firmly bonded to the brass plating wire used as a reinforcing material for hydraulic hoses without deteriorating the characteristics and handleability, and the environmental risk problem caused by nitrosamine generation can be eliminated as much as possible. It can be suitably used as an inner tube rubber.
  • the inner tube rubber of the hose with the rubber composition of the present invention, the inner tube rubber and the brass plating wire of the reinforcing layer are firmly bonded, so that both of them can be peeled off even in severe use. It can be set as the hose excellent in durability without any.
  • the amount of adhesion aid added to increase the cost of rubber has been optimized, so it can be made more cost-effective.
  • rubber hardness increases and workability decreases due to the addition of various adhesion aids.
  • there is no fear of adverse effects on rubber properties other than adhesiveness such as vulcanization rate delay, and there is no environmental risk due to nitrosamine generation as in the case of using conventional thiuram compounds.
  • an appropriate amount of bismaleimide is added as a co-crosslinking agent, the generation of bulges can be more effectively suppressed and a highly reliable hose can be obtained.
  • the rubber composition of the present invention by using a thiuram compound as a vulcanization accelerator, excellent adhesion to a brass plating wire used as a reinforcing material for a hydraulic hose without causing problems of cost and workability. Moreover, the problem of environmental risk due to nitrosamine does not occur as in the case of using a conventional thiuram compound. Furthermore, it is possible to prevent as much as possible the occurrence of bulges seen when using conventional thiuram compounds. Therefore, by using the rubber composition of the present invention for the inner rubber of a hydraulic hose, it is possible to provide a hydraulic hose which is excellent in durability, reliability and cost performance and has little environmental risk.
  • the rubber composition for a hose of the present invention uses a rubber component containing acrylonitrile butadiene rubber (NBR) at a predetermined ratio, and a predetermined amount of the specific thiuram compound represented by the general formula (1) as a vulcanization accelerator. It contains a predetermined amount of phenolic resin, and is particularly suitably used as rubber for forming the inner rubber layer 2 in the hydraulic hose 1 shown in FIG.
  • NBR acrylonitrile butadiene rubber
  • the rubber component includes NBR.
  • the ratio of NBR in the rubber component is 80 parts by mass or more, preferably 90 parts by mass or more, and more preferably 100 parts by mass, out of 100 parts by mass of the rubber component. If the NBR ratio is less than the above range, the adhesiveness may be lowered.
  • the NBR may be appropriately selected from known ones, and is not particularly limited.
  • the amount of acrylonitrile (AN content) contained in the NBR is 28 to 41% by mass, particularly 35 to 41% by mass. A range is preferable. If the AN content exceeds 41% by mass, the low temperature characteristics and fatigue resistance may decrease and the hardness may increase, and if it is less than 28% by mass, the required oil resistance may not be achieved.
  • a known natural or synthetic rubber can be blended. Specifically, butadiene rubber, styrene / butadiene rubber, ethylene / propylene / diene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene / isoprene rubber, acrylonitrile / butadiene rubber, silicone rubber, acrylic rubber, epoxidized natural rubber , Synthetic rubbers such as acrylate butadiene rubbers and the like, and those in which the molecular chain ends of these synthetic rubbers or natural rubbers are modified. One or more of these may be appropriately selected and used. . When the above rubber is blended, it is preferably 20 parts by mass or less, particularly 10 parts by mass or less, out of 100 parts by mass of the rubber component.
  • a thiuram compound represented by the following general formula (1) is used as a vulcanization accelerator.
  • R is an alkyl group or aryl group having 6 or more carbon atoms, and may be different from each other or two or more may be the same.
  • R in the above formula (1) is an alkyl group having 6 or more carbon atoms or an aryl group as described above. As described above, these four Rs may be different from each other, two or more may be the same, or all four Rs may be the same.
  • Such thiuram compounds are not particularly limited, but tetrabenzylthiuram disulfide (TBZTD) and tetrakis (2-ethylhexyl) thiuram disulfide are preferably used.
  • TBZTD tetrabenzylthiuram disulfide
  • 2-ethylhexyl tetrakis (2-ethylhexyl) thiuram disulfide
  • Noxeller TBZTD TBZTD
  • Noxeller TOT-N tetrakis (2-ethylhexyl) thiuram disulfide manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. can be used. Can do.
  • the thiuram compound represented by the general formula (1) is used as a vulcanization accelerator, and can effectively improve the adhesion of the rubber composition to a reinforcing material such as a brass plating wire.
  • nitrosamine is not substantially volatilized from the vulcanized product, and a rubber vulcanized product with low environmental risk can be obtained.
  • the amount of the thiuram compound is 1 to 5 parts by weight, preferably 2 to 4 parts by weight, per 100 parts by weight of the rubber component. If the blending amount is less than 1 part by mass, good adhesiveness cannot be obtained, and a sufficient vulcanization rate cannot be obtained, and the productivity may be adversely affected.
  • the high temperature elastic modulus may be lowered and the generation of bulges may not be sufficiently suppressed.
  • the amount exceeds 5 parts by mass a large amount of bloom tends to occur on the rubber surface after vulcanization, which is disadvantageous in terms of cost.
  • the scorch time is shortened, and the scorch stability may be lowered.
  • the rubber composition of the present invention includes thiazole compounds other than thiuram compounds (2-mercaptobenzothiazole: MBT, dibenzothiazoyl disulfide: MBTS, etc.), guanidine compounds (diesters), and the like without departing from the object of the present invention.
  • thiazole compounds other than thiuram compounds (2-mercaptobenzothiazole: MBT, dibenzothiazoyl disulfide: MBTS, etc.
  • guanidine compounds dieselters
  • -O-tolylguanidine DOTG
  • 1,3-diphenylguanidine DPG, etc.
  • sulfenamide type N-dichloro-2-benzothiazoylsulfenamide: CBS
  • N-tert-butyl-2-benzo A vulcanization accelerator such as thiazolylsulfenamide (BBS, etc.) can also be blended.
  • the blending amount is 2 parts by mass or less with respect to 100 parts by mass of the rubber component, and the total amount with the thiuram compound is 5 parts by mass or less. It is preferable to do so.
  • TMTM tetramethylthiuram monosulfide
  • TETD tetraethylthiuram disulfide
  • TBTD tetrabutylthiuram disulfide
  • the phenolic resin may be novolak type or resol type, and may be unmodified or modified phenolic resin such as cashew nut oil modified, oil modified, rosin modified, etc., but is not particularly limited, such as cashew nut oil modified phenolic resin, etc. Is preferably used.
  • the compounding amount of the phenol resin is 1 to 4 parts by mass, preferably 2 to 3 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount of the phenolic resin is less than 1 part by mass, sufficient adhesiveness may not be obtained. On the other hand, if it exceeds 4 parts by mass, the high-temperature elastic modulus may decrease and bulge generation may not be suppressed. In addition, the scorch time is shortened and the scorch stability is lowered.
  • Adding a large amount of phenolic resin increases the hardness at normal temperature and may lead to a decrease in fatigue resistance.In the present invention, the amount of addition is minimized to minimize the effect. is there. Further, according to the study of the present inventor, it has been found that when phenol resin is added, the hardness at normal temperature increases, while the elastic modulus decreases at a high temperature, which may adversely affect the bulge. Therefore, in the present invention, although not particularly limited, it is preferable to add an appropriate amount of bismaleimide in order to improve the high temperature elastic modulus and prevent bulge generation more effectively.
  • a bulge is a phenomenon in which a rubber member swells in the vicinity of a caulking portion with a metal fitting when used under high temperature conditions (about 80 ° C or higher), but when this swell increases, eventually rubber breaks and cracks occur. In addition, the contents may leak from the hose. In this case, if the caulking rate is lowered to suppress this bulge, the fixed state and liquid tightness of the hose will be insufficient, which will also cause leakage and hose disconnection, and bulge is one of the basic performance of the hose. is there.
  • the amount of reinforcing material and crosslinking agent should be increased.
  • this causes a decrease in workability and a decrease in heat resistance due to an increase in viscosity.
  • bismaleimide as a co-crosslinking agent, the high temperature elastic modulus can be improved without reducing heat resistance and processing workability, and bulge generation can be effectively suppressed.
  • the addition amount of this bismaleimide is preferably 1 to 5 parts by mass, more preferably 2 to 4 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount is less than 1 part by mass, a sufficient effect of improving the high-temperature elastic modulus cannot be obtained. On the other hand, adding more than 5 parts by mass only increases the cost, and further improvement of the effect is obtained. I can't.
  • the type of bismaleimide is not limited and may be appropriately selected from known co-crosslinking agents. For example, N, N′-m-phenylene dimaleimide (Ouchi Shinsei Chemical Co., Ltd., “Barnock”) may be used.
  • N, N '-(4,4'-diphenylmethane) bismaleimide (Daiwa Kasei Kogyo Co., Ltd.” BMI-RB "), N, N'-1,2-phenylenebismaleimide, N, N' -1,3-phenylenebismaleimide, N, N′-1,4-phenylenebismaleimide, N, N ′-(4,4′-diphenylmethane) bismaleimide, 2,2-bis [4- (4-maleimide) Phenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the like are preferably used, and in particular, N, N′-m-phenylene dimaleimide, N, N′— 4,4'-diphenylmethane) bismaleimide is more preferably used.
  • sulfur can be used as a crosslinking agent.
  • the blending amount is preferably 1.5 to 3 parts by mass, particularly 1.5 to 2.5 parts by mass, and more preferably 1.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount exceeds 3 parts by mass, good adhesiveness can be obtained, but the heat resistance may decrease, and if it is less than 1.5 parts by mass, the adhesiveness may decrease. There is.
  • zinc oxide can be blended as a vulcanization accelerator.
  • the blending amount is preferably 0.5 to 10 parts by mass, particularly 0.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount exceeds 10 parts by mass, the adhesiveness may be lowered. If the blending amount is less than 0.5 parts by mass, the effect of improving the vulcanization rate may be hardly obtained.
  • the mixing ratio of sulfur and zinc white is 0.4 or more, particularly 2.0 or more.
  • the upper limit is not particularly limited, but is preferably 6.0 or less, particularly 3.0 or less.
  • the above rubber component as long as it does not impair the effects of the present invention, if necessary, other crosslinking agents (vulcanizing agents), vulcanization accelerators and vulcanization acceleration assistants, Carbon used, anti-aging agent, plasticizer, petroleum resin, vulcanization retarder, waxes, antioxidant, filler, foaming agent, oil, lubricant, tackifier, UV absorber, dispersant, phase Additives such as a solubilizer and a homogenizer can be appropriately blended.
  • crosslinking agents vulcanizing agents
  • vulcanization accelerators and vulcanization acceleration assistants Carbon used, anti-aging agent, plasticizer, petroleum resin, vulcanization retarder, waxes, antioxidant, filler, foaming agent, oil, lubricant, tackifier, UV absorber, dispersant, phase Additives such as a solubilizer and a homogenizer can be appropriately blended.
  • Known carbon can be used.
  • carbon blacks such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT can be mentioned.
  • SRF can be preferably used.
  • these carbon blacks may be used individually by 1 type, and may use 2 or more types together.
  • the blending amount of the carbon black is preferably 50 to 150 parts by mass, particularly 80 to 120 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount exceeds 150 parts by mass, the viscosity of the unvulcanized rubber may increase too much, which may reduce kneading, rolling, and extrusion workability. If the blending amount is less than 50 parts by mass, the strength necessary for a hydraulic hose is increased. May not be obtained.
  • anti-aging agent known ones can be used, and are not particularly limited, but one or more of phenol-based anti-aging agent, imidazole-based anti-aging agent, amine-based anti-aging agent and the like are used. Can be used.
  • the blending amount of the anti-aging agent is preferably 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
  • plasticizer known ones can be used and are not particularly limited. Specifically, process oils such as aromatic oil, naphthenic oil, paraffin oil, palm oil, castor oil, etc. Vegetable oils, synthetic oils such as alkylbenzene oil, and ester plasticizers such as DOA (dioctyl adipate). These can be used alone or in combination of two or more.
  • the blending amount of the plasticizer is preferably 5 to 15 parts by mass with respect to 100 parts by mass of the rubber component.
  • the petroleum resin known aromatic hydrocarbon resins, aliphatic hydrocarbon resins and the like can be used. These petroleum resins may be used alone or in combination of two or more.
  • the blending amount of the petroleum resin is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component.
  • vulcanization retarder known ones can be used and are not particularly limited, and examples thereof include N-cyclohexylthiophthalimide (Santogard PVI: manufactured by Monsato).
  • the blending amount of the vulcanization retarder is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the rubber component.
  • the rubber composition of the present invention there is no particular limitation on the blending method of each of the above components, and all the component raw materials may be blended and kneaded at once, and each component may be divided into two or three stages. You may mix
  • vulcanization conditions for curing the rubber composition are not particularly limited, but vulcanization conditions of 140 to 180 ° C. for 10 to 90 minutes can be usually employed.
  • a usual method can be employed. For example, as shown in FIG. 1, a rubber-made inner rubber layer 2 (inner tube rubber) filled with hydraulic oil, a reinforcing layer 3 for withstanding the pressure of the hydraulic oil, and the reinforcing layer 3 and the inner surface.
  • the hydraulic hose 1 in which the outer rubber layer 4 (outer rubber) that prevents the rubber layer 2 from being damaged is sequentially laminated, the hydraulic hose 1 can be manufactured by the following method.
  • the rubber composition of the present invention is extrusion-molded on the outer side of a core (mandrel) having the same diameter as the inner diameter of the hose to cover the mandrel, thereby forming an inner rubber layer (inner tube rubber) 2 (inner Tube extrusion process).
  • a predetermined number of brass-plated wires are knitted outside the inner rubber layer 2 formed in the inner tube extrusion step, and a reinforcing layer 3 is laminated (knitting step).
  • the rubber composition to be formed is extruded to form an outer rubber layer (outer rubber) 4 (outer extrusion process).
  • the outer surface of the outer rubber layer 4 formed in the jacket extrusion step is coated with a resin (resin mold coating step), and vulcanized under normal conditions (vulcanization step). After vulcanization, the above-mentioned coating resin is peeled off (resin mold peeling step), and the mandrel is removed (mandrel extraction step), whereby a hydraulic hose 1 having a reinforcing layer 3 between the inner tube rubber 2 and the outer jacket rubber 4 It becomes.
  • the hydraulic hose 1 thus obtained is excellent in durability that the inner tube rubber 2 and the brass plating wire of the reinforcing layer 3 are firmly bonded to each other so that they do not peel off even in severe use. It will be.
  • the structure of the hydraulic hose 1 may be a three-layer structure in which the inner tube rubber 2, the reinforcing layer 3 and the outer cover rubber 4 are sequentially laminated from the inside as described above.
  • the reinforcing layer may be a two-layer structure, and a five-layer structure in which an intermediate layer (intermediate rubber) is disposed between the two reinforcing layers.
  • Example 1 The rubber composition for hose was kneaded according to a conventional method with the composition shown in Example 1 in Table 1 below, and this was used as the basic composition. At that time, in the kneading operation, first, each compounding agent except the vulcanizing agent was added to the raw rubber and kneaded with a Banbury mixer or a kneader (non-processing kneading), which was taken out of the kneader and cooled sufficiently. Thereafter, the remaining compounding agent containing the vulcanizing agent was added, and the mixture was returned to the kneader and kneaded again (professional kneading processing kneading).
  • NBR “JSR N230S” manufactured by JSR Corporation (AN content 35% by mass)
  • Carbon black SRF grade carbon black, "Asahi # 50” manufactured by Asahi Carbon Co., Ltd.
  • Anti-aging agent “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
  • Petroleum resin hydrocarbon fraction polymer having 4 to 5 carbon atoms, "ESCOREZ1102” manufactured by Tonen Chemical Co., Ltd.
  • Plasticizer DOA (dioctyl adipate), “Sanso Sizer DOA” manufactured by Shin Nippon Rika Co., Ltd.
  • Vulcanization retarder “SantogardPVI” manufactured by Monsato Phenol resin: “Sumilite resin PR-12687” manufactured by Sumitomo Bakelite Co., Ltd.
  • Bismaleimide “Barunok PM” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • the rubber composition of Example 1 according to the present invention has a low environmental risk using TBZTD that does not generate nitrosamines, and exhibits excellent adhesion to a brass-plated wire, The scorch time is good, no bloom is seen, and the appearance of the vulcanizate is excellent. Further, the elastic modulus at a high temperature (150 ° C.) is sufficient, and the occurrence of bulge can be prevented well.
  • the rubber composition of Comparative Example 1 which is a conventional blend, uses tetramethylthiuram monosulfide (TMTM), which is feared to generate nitrosamine as a vulcanization accelerator, and therefore has a high environmental risk. Yes. Further, the high-temperature elastic modulus is somewhat low, and the possibility of bulging is higher than that in Example 1.
  • Examples 2 and 3 Comparative Examples 2 to 7
  • the adhesiveness, high temperature elastic modulus, scorch time, and appearance (bloom) in each blending composition were examined.
  • the case where the compounding quantity of vulcanization accelerator TBZTD was changed was examined.
  • the results are shown in Table 2.
  • Example 1 basic composition
  • Basic blend vulcanization accelerator TOT Tetrakis (2-ethylhexyl) thiuram disulfide, “Noxeller TOT-N” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Comparative Examples 8 and 9 in Table 3 above when the phenol resin is not blended, sufficient adhesiveness cannot be obtained, and the object of the present invention cannot be achieved. Conversely, as shown in Comparative Examples 10 and 11, when there is too much phenol resin, the high temperature elastic modulus is lowered and the scorch time is also shortened. On the other hand, as in Examples 1 and 4 to 6, it was confirmed that excellent adhesiveness was obtained even when TBZTD was used as a vulcanization accelerator by using an appropriate amount of a phenol resin. Further, comparing Example 10 containing no bismaleimide with other Examples 1 and 4 to 9 clearly shows that the addition of bismaleimide improves the high-temperature elastic modulus.
  • TOT tetrakis (2-ethylhexyl) thiuram disulfide

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  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
PCT/JP2014/052890 2013-02-13 2014-02-07 ホース用ゴム組成物及びホース Ceased WO2014126015A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2014217187A AU2014217187B2 (en) 2013-02-13 2014-02-07 Rubber composition for hoses, and hose
CN201480008795.9A CN104995249B (zh) 2013-02-13 2014-02-07 软管用橡胶组合物和软管
US14/766,897 US20150368448A1 (en) 2013-02-13 2014-02-07 Rubber composition for hoses, and hose

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US20150368448A1 (en) 2015-12-24
AU2014217187B2 (en) 2016-09-15
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