WO2014168129A1 - 成型ゴムホースの製造方法 - Google Patents
成型ゴムホースの製造方法 Download PDFInfo
- Publication number
- WO2014168129A1 WO2014168129A1 PCT/JP2014/060142 JP2014060142W WO2014168129A1 WO 2014168129 A1 WO2014168129 A1 WO 2014168129A1 JP 2014060142 W JP2014060142 W JP 2014060142W WO 2014168129 A1 WO2014168129 A1 WO 2014168129A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vulcanization
- rubber hose
- rubber
- layer
- degree
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/0266—Local curing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
- B29K2105/243—Partially cured
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
- B29L2023/004—Bent tubes
-
- 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
Definitions
- the present invention relates to a method for producing a molded rubber hose having a rubber layer used for a refrigerant transport hose or the like in an air conditioning system of an automobile.
- a multilayer hose having a rubber layer (also simply referred to as “rubber hose”) has been used as a refrigerant transport hose or the like in an air conditioning system of an automobile.
- rubber hose also simply referred to as “rubber hose”
- the space for arranging the hose has been limited, and a molded rubber hose formed by bending the rubber hose into a shape matching the space is used.
- the rubber hose used for the refrigerant transport hose is required to have pressure resistance, and usually has an inner tube rubber layer, a reinforcing layer, and an outer rubber layer.
- the hose in the semi-vulcanized state in a predetermined bent mold Secondary vulcanization is carried out in a state where the shape is maintained by fitting, for example, to produce a molded rubber hose bent into a desired shape.
- the straight hose in a semi-cured state is bent and subjected to secondary vulcanization.
- the shape is stable following the mold. Therefore, in a mold with the same bent shape as the desired shape, the bent portion may spread, and therefore, a plurality of molds with a shape bent larger than the desired bent shape are manufactured in anticipation of the expansion of the bent portion.
- a product that does not meet the standards may be produced, resulting in a decrease in product yield and an increase in cost and environmental load.
- the primary vulcanization is usually performed by treating a non-vulcanized rubber hose in a container in which a heat medium such as air or steam is adjusted to a temperature at which the rubber layer is not completely vulcanized for a predetermined time. At this time, if the primary vulcanization is insufficient, the outer rubber surface may be damaged when fitted into the mold, or the outer rubber may be deformed due to the mold, etc. If the vulcanization progresses too much, there is a case where the desired shape cannot be obtained even if the secondary vulcanization is performed thereafter, and it is difficult to set the conditions for the primary vulcanization.
- a heat medium such as air or steam
- the outer rubber layer has two layers, and the optimum vulcanization time for the outer layer is shorter than the optimum vulcanization time for the inner layer.
- a method for facilitating optimization of a semi-vulcanized state by primary vulcanization by preparing a blend of the rubber composition of each layer and defining a primary heating method has been developed.
- an object of the present invention is to provide a rubber hose in an appropriate semi-vulcanized state easily by primary vulcanization in a method for producing a molded rubber hose including a two-stage vulcanization process, and at the time of secondary vulcanization. It is providing the manufacturing method which can improve shape stability.
- the purpose of the above is to obtain a semi-vulcanized rubber hose by primary vulcanization of an unvulcanized rubber hose formed on the outer periphery of the mandrel, and to hold the semi-vulcanized rubber hose in a desired shape to obtain a secondary
- a method for producing a molded rubber hose comprising a step of obtaining a molded rubber hose by vulcanization, wherein the unvulcanized rubber hose has an unvulcanized rubber layer on the outermost periphery, and the primary vulcanization is performed by the unvulcanized rubber hose.
- a rubber hose in a semi-vulcanized state in which the vulcanization degree in the vicinity of the outer peripheral side surface of the rubber hose is higher than the vulcanization degree in the vicinity of the inner peripheral side surface is obtained by irradiating the outer peripheral side of the rubber layer with near infrared rays and heating. This is achieved by a method of manufacturing a molded rubber hose characterized by the above.
- the outer surface of the unvulcanized rubber layer is The temperature can be raised rapidly.
- the temperature rise on the mandrel side (that is, the inner peripheral side) of the unvulcanized rubber layer which is difficult for near infrared rays to reach, is suppressed from the outer peripheral side.
- Preferred embodiments of the method for producing a molded rubber hose according to the present invention are as follows.
- the unvulcanized rubber hose has a plurality of unvulcanized rubber layers, and the vulcanization degree of the outermost rubber layer after the primary vulcanization is higher than the vulcanization degree of the other rubber layers. It has become. In this way, in the primary vulcanization, the degree of vulcanization of one rubber layer is not partially controlled, but is controlled for each rubber layer. It is possible to obtain a semi-vulcanized rubber hose that is high and has a low degree of vulcanization near the inner peripheral surface.
- the “other rubber layer” means a rubber layer inside the outermost rubber.
- the shape stability of the molded rubber hose can be further improved.
- the difference between the vulcanization degree of the outermost rubber layer and the vulcanization degree of other rubber layers is 10% or more and 70% or less. If the difference in the degree of vulcanization is too large, the degree of vulcanization of the outermost rubber layer may be too large and the moldability may deteriorate. If it is too small, the degree of vulcanization of the other rubber layer will be too large and the moldability Can be very bad.
- the difference between the vulcanization degree of the outermost rubber layer and the vulcanization degree of other rubber layers is 30% or more and 50% or less. A molded rubber hose with better moldability can be obtained.
- the primary vulcanization heating is performed so that the temperature on the outer peripheral surface of the outermost unvulcanized rubber layer is 130 to 200 ° C. If the temperature is too low, vulcanization will not proceed, and if it is too high, the rubber component may deteriorate.
- the primary vulcanization is performed. By forming a transparent thermoplastic resin coating on the outer periphery of the rubber layer, foaming during vulcanization can be prevented, and the coating can transmit near infrared rays. The outer peripheral surface can be sufficiently heated.
- the unvulcanized rubber hose has a reinforcing layer.
- the method for producing a molded rubber hose of the present invention is particularly effective.
- the secondary vulcanization is performed by fitting a semi-vulcanized rubber hose into a mold, holding it in a predetermined shape, and heating it. Thereby, the molding accuracy can be further improved.
- FIG. 1 It is a schematic sectional drawing which shows a typical example of the manufacturing method of the shaping
- FIG. 1 is a schematic cross-sectional view showing a typical example of a method for producing a molded rubber hose of the present invention.
- FIG. 1 (a) shows the steps up to the primary vulcanization
- FIG. 1 (b) shows the molding steps. Show.
- the inner tube rubber layer is formed on the outer periphery of the mandrel 11 by extruding the rubber composition for the inner tube rubber layer from the extruder 31.
- a reinforcing layer is formed on the outer periphery of the inner tube rubber layer by, for example, winding a fiber made of polyethylene terephthalate resin (PET) in a spiral shape with a knitting machine 32. Then, the rubber composition for the outer rubber layer is extruded from the extruder 33 to the outer periphery of the reinforcing layer, the outer rubber layer is formed, and the unvulcanized rubber hose 21 is formed.
- PET polyethylene terephthalate resin
- the unvulcanized rubber hose 21 formed on the outer periphery of the mandrel is introduced into the near-infrared irradiation device 34, heated, and subjected to primary vulcanization so that the vicinity of the outer surface of the rubber hose (in the description of FIG. 1 above)
- a rubber hose 22 in a semi-vulcanized state is obtained, in which the degree of vulcanization of the outer rubber layer is higher than the degree of vulcanization in the vicinity of the inner peripheral surface (inner pipe rubber layer in the description of FIG. 1).
- the near-infrared irradiation device 34 may be any device as long as it can irradiate near-infrared rays over the entire outer peripheral side of the unvulcanized rubber hose 21 for a predetermined time.
- a plurality of near infrared lamps 35 are arranged inside a tubular body 36 having a mirror inner surface.
- Near-infrared irradiation may be continuous or batch-type. In the case of the continuous type, the irradiation time can be controlled by adjusting the length of the tubular body 36 and the conveyance speed of the unvulcanized rubber hose 21.
- the outer peripheral surface temperature of the rubber hose 21 can be rapidly increased.
- the temperature rise is suppressed more than in the vicinity of the outer peripheral surface.
- the heating time is long and the temperature rises in the same way for the entire unvulcanized rubber hose, so the degree of vulcanization near the outer peripheral surface and the inner peripheral surface
- the degree of vulcanization in the vicinity of the outer peripheral surface of the rubber hose is near the inner peripheral surface.
- a rubber hose 22 in a semi-vulcanized state having a higher vulcanization degree can be easily obtained.
- the range near the outer peripheral surface of the rubber hose and the vicinity of the inner peripheral surface is not particularly limited as long as the object of the present invention can be achieved, but the vicinity of the outer peripheral surface is generally from the outer surface of the rubber hose to the inner surface. It is in the range of 0.01 to 1.0 mm, preferably 0.01 to 0.5 mm, toward the circumferential side, and the vicinity of the inner circumferential surface side surface is 0.00 mm from the inner circumferential surface of the rubber hose toward the outer circumferential side.
- the range is 01 to 1.0 mm, preferably 0.01 to 0.5 mm.
- the rubber hose 22 in a semi-vulcanized state is usually temporarily stored after the mandrel is extracted (demandrel), wound around a drum, and subjected to the secondary vulcanization process (see FIG. 1 (a)).
- the semi-vulcanized rubber hose 22 is cut out to a desired length and fitted into a mold 37 to keep it in a predetermined shape, and put in the vulcanizer 38 in that state for a predetermined time. Secondary vulcanization is achieved by heating. Thereafter, the molded rubber hose 23 is manufactured by removing the mold (FIG. 1B).
- any method may be used to hold the semi-vulcanized rubber hose 22 in a predetermined shape, and a bent mandrel or a plurality of clamps may be used. In order to further improve the molding accuracy, it is preferable to fit into the mold 37 and hold it in a predetermined shape as shown in FIG.
- the vulcanizer 38 any known vulcanizer may be used. For example, a heating furnace or the like that controls and heats the temperature of a heat medium such as air or steam can be used.
- the unvulcanized rubber hose 21 only needs to have an unvulcanized rubber layer (outer rubber layer in the description of FIG. 1 above) on the outermost periphery, and the configuration on the inner periphery side thereof is as follows. Any thing is good. That is, the inner tube rubber layer and the reinforcing layer in the description of FIG. 1 may not be provided. Conversely, even if a resin layer is formed on the inner peripheral side of the inner tube rubber layer in the description of FIG. Another rubber layer, a reinforcing layer, an adhesive layer, or the like may be further formed between the layer and the outer rubber layer.
- the vicinity of the inner peripheral side surface of the rubber hose refers to the rubber layer formed on the innermost peripheral side in the rubber layer (see FIG. 1 above). In the description, it means the vicinity of the inner peripheral surface of the inner tube rubber layer).
- primary vulcanization it is easier to control the degree of vulcanization for each rubber layer than to control the degree of vulcanization in the vicinity of the outer peripheral surface and the inner peripheral surface of one rubber layer.
- the unvulcanized rubber hose 21 is as described in FIG. It is preferable to have a plurality of unvulcanized rubber layers, and after the primary vulcanization, the degree of vulcanization of the outermost rubber layer (the outer rubber layer in the description of FIG. 1) It is preferable that the degree of vulcanization of the rubber layer (in the above description of FIG. 1, the inner tube rubber layer) is higher.
- the difference between the vulcanization degree of the outermost rubber layer and the vulcanization degree of the other rubber layer is 10% or more. It is preferably 10% or more and 70% or less, more preferably 30% or more and 50% or less. If the difference in the degree of vulcanization is too small, the moldability of the molded rubber hose may become very bad. If the difference in the degree of vulcanization is too large, the degree of vulcanization on the outer peripheral side will be too large and the moldability will deteriorate. There is. By setting it as the difference of said vulcanization degree, the molding rubber hose which is more excellent in moldability can be obtained.
- the degree of vulcanization of the outermost rubber layer (for example, the outer rubber layer) is too large, the moldability may be deteriorated, and if it is too small, it may be easily damaged.
- the vulcanization degree of the rubber layer is preferably 30 to 80%.
- the vulcanization degree of the other rubber layer (for example, the inner tube rubber layer) is too small, the rubber layer may be too soft, and if it is too large, the moldability may be very poor.
- the vulcanization degree of the rubber layer is preferably 10 to 40%.
- the degree of vulcanization is the minimum value M L of the torque of the rubber obtained by Curelastometer vulcanization degree 0%, the maximum value M H and vulcanization degree of 100%, the highest and lowest values This is calculated from the difference.
- the layer thickness of the outermost rubber layer (the outer rubber layer in the description of FIG. 1 above) and the inner tube rubber layer is not particularly limited, but can be, for example, 0.5 to 2.5 mm.
- the layer thickness of the reinforcing layer may be set as appropriate, and can be set to 0.5 to 2.5 mm, for example.
- the temperature of primary vulcanization can be freely set according to the proper vulcanization temperature of the rubber composition to be used. If it is too low, vulcanization is difficult to proceed. If it is too high, deterioration of the rubber component and use of resin fibers such as PET fibers for the reinforcing layer may damage the resin fibers. Heating is preferably performed so that the temperature on the outer peripheral side surface of the unvulcanized rubber layer is 130 to 200 ° C, and more preferably 130 to 180 ° C.
- the unvulcanized rubber layer on the outermost periphery of the unvulcanized rubber hose 21 may be exposed to the atmosphere as shown in FIG. 1, but may be accompanied by foaming depending on the rubber composition. .
- FIG. 2 is a schematic cross-sectional view showing an example of a preferred embodiment of the method for producing a molded rubber hose of the present invention, and shows a case where the process of the broken line part in FIG. 1 is changed. That is, as described in FIG. 1 above, after the unvulcanized hose 21 is formed on the outer periphery of the mandrel, a transparent thermoplastic resin composition (plastic mold) is fed from the extruder 39 to the outer periphery of the outermost outer cover rubber layer. Resin composition) is extruded and then passed through the cooling device 40 to form a covering (plastic mold 12) made of a transparent thermoplastic resin. Thereafter, as illustrated in FIG.
- a transparent thermoplastic resin composition plastic mold
- Resin composition is extruded and then passed through the cooling device 40 to form a covering (plastic mold 12) made of a transparent thermoplastic resin.
- the plastic mold 12 is made of a transparent thermoplastic resin and can transmit near infrared rays, the outer peripheral surface of the outermost outer cover rubber layer can be sufficiently heated. By covering with the plastic mold 12, foaming during vulcanization of the rubber component can be prevented. In particular, as described later, when an organic peroxide is used as a vulcanizing agent, oxygen that becomes a vulcanization inhibiting factor can be blocked. In addition, since the plastic mold 12 is usually low in flexibility, it is removed before the secondary vulcanization.
- the production method of the present invention can be applied to any hose as long as it is a molded rubber hose having a rubber layer.
- a molded rubber hose having a reinforcing layer as shown in FIG. 1 is manufactured, a one-step vulcanization method in which a rubber composition is directly injected into a mold cannot be adopted, and a two-step vulcanization process is performed. Therefore, the production method of the present invention is effective.
- FIG. 3 As a representative example of the molded rubber hose obtained by the production method of the present invention, an example of the configuration of a refrigerant transport hose of an automobile air conditioner is shown in FIG.
- the refrigerant transport hose shown in FIG. 3 has an inner surface resin layer 1, an inner tube rubber layer 2, a reinforcing layer 3, and an outer cover rubber layer 4.
- the inner surface resin layer 1 is a layer for preventing volatilization of the transported refrigerant. Since such a refrigerant transport hose is required to have a complicated bent shape in accordance with the space in the engine room of the automobile, the method for producing a molded rubber hose of the present invention is a particularly effective molded rubber hose.
- the rubber component used in the composition forming the rubber layer is not particularly limited.
- natural rubber butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber (HNBR), butyl rubber, brominated isobutylene-paramethylstyrene (BIMS), ethylene-propylene rubber (EPM), ethylene- Propylene-diene rubber (EPDM), chlorosulfonated polyethylene, acrylic rubber (ACM), ethylene-acrylic copolymer (AEM), silicone rubber, fluororubber, urethane rubber, and the like, and mixtures thereof can be used.
- natural rubber butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber (HNBR), butyl rubber, brominated isobutylene-paramethylstyrene (BIMS), ethylene-propylene rubber (EPM
- a well-known thing can be used also as a vulcanizing agent.
- an organic peroxide such as a sulfur-based vulcanizing agent, dicumyl peroxide, dibutyl peroxide, 1,3 bis- (butylperoxy-isopropyl) -benzene can be blended.
- the composition for forming the outermost rubber layer (the outer rubber layer in FIG. 1) has natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, as a rubber component so as to have heat resistance after vulcanization.
- Nitrile rubber hydrogenated nitrile rubber (HNBR), butyl rubber, brominated isobutylene-paramethylstyrene (BIMS), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), acrylic rubber (ACM), ethylene-acrylic
- BIMS hydrogenated nitrile rubber
- EPM ethylene-propylene rubber
- EPDM ethylene-propylene-diene rubber
- ACM acrylic rubber
- ethylene-acrylic Using a copolymer (AEM) alone or a mixture thereof, an organic peroxide such as dicumyl peroxide, dibutyl peroxide, 1,3 bis- (butylperoxy-isopropyl) -benzene was added as a vulcanizing agent. Those are preferred.
- the reinforcing layer there is no particular limitation when forming the reinforcing layer.
- known materials such as PET, vinylon, polyamide, polyethylene naphthalate (PEN), resin fibers such as aramid, and metal wires made of steel can be used.
- PEN polyethylene naphthalate
- resin fibers such as aramid
- limiting in particular also when forming an inner surface resin layer It can select in consideration of gas barrier property etc.
- a polyamide resin such as nylon
- an ethylene-vinyl alcohol copolymer such as polyethylene-vinyl alcohol copolymer
- a fluororesin, or the like can be used.
- the output and wavelength in near infrared irradiation are not particularly limited as long as the effects of the present invention are obtained.
- Any near infrared lamp may be used as long as it can irradiate light having a wavelength of 800 to 3000 nm.
- a halogen heater can be used. If the wavelength is smaller than 800 nm, the degree of vulcanization will not be sufficiently increased, and if it is larger than 3000 nm, it will be absorbed by the covering and the degree of vulcanization of the rubber itself will not be sufficiently increased.
- the mandrel can be used without any particular limitation.
- a thermoplastic resin having heat resistance that does not deform at the vulcanization temperature and flexibility is preferable.
- a polyamide resin nylon or the like
- a polyphenylene oxide resin a fluororesin, a rubber, or the like
- the transparent thermoplastic resin is not particularly limited as long as it has a predetermined hardness and transparency at the vulcanization temperature and can prevent foaming of the rubber layer.
- a known transparent thermoplastic resin can be used.
- polyolefin (TPX) obtained by polymerizing 4-methylpentene-1, polyamide, polypropylene or the like can be used.
- Example 1 After TPX was extruded to the outer periphery of the outer rubber layer of the unvulcanized rubber hose, it was cooled to form a plastic mold (see FIG. 2). A temperature change of the surface of each layer was examined when a primary vulcanization was performed by irradiating near infrared rays on a sample having a diameter of 30 mm and a length of 300 mm obtained by cutting an unvulcanized rubber hose formed on the outer periphery of this plastic mold ( Example 1). Moreover, about the same sample, the temperature change of the surface of each layer at the time of heating in the heating furnace which uses air as a heat medium and performing primary vulcanization was investigated (comparative example 1).
- Example 1 in which primary vulcanization was performed using near infrared rays, the surface temperature of the plastic mold and the outer rubber layer reached 170 ° C. in 26 seconds. The surface temperature of the tube rubber layer was 85 ° C.
- Comparative Example 1 in which primary vulcanization was performed using a heating furnace, the temperature increased generally more slowly than in Example 1, and the temperature of the outer rubber layer surface and the temperature of the inner tube rubber layer surface were increased. No significant difference was observed between the two, and the time for both to reach 160 ° C. was about 20 minutes.
- the vulcanization degree of the outer rubber layer is 60%. Yes, the vulcanization degree of the inner tube rubber layer was 30%.
- the rubber hose sample in the semi-vulcanized state after the primary vulcanization of Comparative Example 1 has a degree of vulcanization of the outer rubber layer of 60. %, And the vulcanization degree of the inner tube rubber layer was 80%.
- the method for calculating the degree of vulcanization is as described above.
- the semi-vulcanized rubber hose of Example 1 and Comparative Example 1 was fitted into an S-shaped mold, placed in an air circulation type heating furnace, and heated at 160 ° C. for 30 minutes for secondary vulcanization. After cooling, the mold was removed to obtain a molded rubber hose (see FIG. 1B). None of the obtained molded rubber hoses were damaged on the surface, but the molded hose of Example 1 was a molded hose with less bending part return and higher shape stability than the molded rubber hose of Comparative Example 1. there were.
- the degree of vulcanization in the vicinity of the outer peripheral surface of the rubber hose (the outer cover rubber layer in the first embodiment) is in the vicinity of the inner peripheral surface (example).
- the rubber hose in a semi-cured state which is higher than the degree of vulcanization of the inner tube rubber layer
- the rubber layer surface is hardly damaged or deformed during secondary vulcanization, and the shape of the molded rubber hose is stable. It was shown that the performance can be improved.
- Mandrel 12 Plastic mold 21 Unvulcanized rubber hose 22 Semi-vulcanized rubber hose 23 Molded rubber hose 31, 33, 39 Extruder 32 Knitting machine 34 Near infrared irradiation device 35 Near infrared lamp 36 Tubular body 37 Mold 38 Vulcanization device 40 Cooling device
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Electromagnetism (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Description
(2)上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、10%以上である。成型ゴムホースの形状安定性をより向上させることができる。
(3)上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、10%以上、70%以下である。加硫度の差が大き過ぎると最外周のゴム層の加硫度が大きすぎて成型性が悪くなる場合があり、小さ過ぎると、他のゴム層の加硫度が大きくなり過ぎて成型性が非常に悪くなる場合がある。
(4)上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、30%以上、50%以下である。より成型性に優れる成型ゴムホースを得ることができる。
(5)前記1次加硫において、最外周の未加硫のゴム層の外周側表面の温度が130~200℃になるように加熱する。温度が低過ぎると加硫が進まず、高過ぎるとゴム成分が劣化する場合がある。
(6)前記未加硫ゴムホースの最外周の未加硫のゴム層の外周に、透明熱可塑性樹脂製の被覆体を形成した後、前記1次加硫を行う。ゴム層の外周に透明熱可塑性樹脂製の被覆体を形成することで、加硫時の発泡を防止することができ、また、上記被覆体は近赤外線を透過させることができるので、ゴム層の外周側表面を十分に加熱することができる。
(7)前記未加硫ゴムホースが、補強層を有する。 本発明の成型ゴムホースの製造方法が特に有効である。
(8)前記2次加硫を、半加硫状態のゴムホースを金型に嵌め込んで所定の形状に保持して加熱することで行う。これにより、更に成型精度を向上することができる。
[実施例1及び比較例1]
マンドレルの外周に、押し出し機から内管ゴム層用のブチルゴム組成物を押し出して内管ゴム層(層厚;1.3mm)を形成し、その外周に編み上げ機によりPET繊維をスパイラル状に編み上げて補強層(層厚;1.6mm)を形成し、その外周に外被ゴム層用のEPDM組成物(有機過酸化物配合)を押し出し、外被ゴム層(層厚;1.1mm)を形成し、未加硫のゴムホースを得た(図1(a)参照)。次に、未加硫のゴムホースの外被ゴム層の外周に、TPXを押し出した後、冷却し、プラスチックモールドを形成した(図2参照)。このプラスチックモールドが外周に形成された未加硫のゴムホースを切断した直径30mm×長さ300mmのサンプルに対して近赤外線照射して1次加硫する際の各層の表面の温度変化を調べた(実施例1)。また、同様なサンプルについて、空気を熱媒体とする加熱炉中で加熱して1次加硫する際の各層の表面の温度変化を調べた(比較例1)。
[実施例2~13、及び比較例2~3]
上記実施例1と同様なサンプルについて、外被ゴム層と内管ゴム層の加硫度を表1に示したようになる条件で、1次加硫を行った後、上記と同様に2次加硫を行い、成型ゴムホースの成型性及び外観を評価した。成型性は、スプリングバック(屈曲部の戻り)がほとんどなく、成型が容易、また成型に伴う不具合(ゴムの肉厚のばらつき等)がない場合を◎、スプリングバックが多少あるが、成型可能であり、また成型に伴う不具合がほとんどない場合を○、スプリングバックがあり、成型がやや難しく、また成型に伴う不具合が散見される場合を△、正常に成型できない、成型に伴う不具合がある場合を×とした。外観は、傷及び型当りによる凹みがほとんどない場合を◎、型当りによる小さな凹みが僅かにつく場合を○、傷及び型当たりによる小さな凹みがつく場合を△、目立つ傷及び型当たりによる大きな凹みがつく場合を×とした。結果を表1に示す。
12 プラスチックモールド
21 未加硫ゴムホース
22 半加硫状態のゴムホース
23 成型ゴムホース
31、33、39 押し出し機
32 編み上げ機
34 近赤外線照射装置
35 近赤外線ランプ
36 管状体
37 金型
38 加硫装置
40 冷却装置
Claims (9)
- マンドレルの外周に形成した未加硫ゴムホースを1次加硫して半加硫状態のゴムホースを得る工程、及び、
半加硫状態のゴムホースを、所望の形状に保持して2次加硫して成型ゴムホースを得る工程を含む成型ゴムホースの製造方法であって、
未加硫ゴムホースが、最外周に未加硫のゴム層を有し、
前記1次加硫を、前記未加硫のゴム層の外周側に近赤外線を照射して加熱することにより行い、ゴムホースの外周側表面近傍の加硫度が、内周側表面近傍の加硫度より高い半加硫状態のゴムホースを得ることを特徴とする成型ゴムホースの製造方法。 - 前記未加硫ゴムホースが、複数の未加硫のゴム層を有し、
前記1次加硫後の最外周のゴム層の加硫度が、他のゴム層の加硫度より高くなっている請求項1に記載の成型ゴムホースの製造方法。 - 上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、10%以上である請求項2に記載の成型ゴムホースの製造方法。
- 上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、10%以上、70%以下である請求項2に記載の成型ゴムホースの製造方法。
- 上記最外周のゴム層の加硫度と、他のゴム層の加硫度との差が、30%以上、50%以下である請求項2に記載の成型ゴムホースの製造方法。
- 前記1次加硫において、最外周の未加硫のゴム層の外周側表面の温度が130~200℃になるように加熱する請求項1~5のいずれか1項に記載の成型ゴムホースの製造方法。
- 前記未加硫ゴムホースの最外周の未加硫のゴム層の外周に、透明熱可塑性樹脂製の被覆体を形成した後、前記1次加硫を行う請求項1~6のいずれか1項に記載の成型ゴムホースの製造方法。
- 前記未加硫ゴムホースが、補強層を有する請求項1~7のいずれか1項に記載の成型ゴムホースの製造方法。
- 前記2次加硫を、半加硫状態のゴムホースを金型に嵌め込んで所定の形状に保持して加熱することで行う請求項1~8のいずれか1項に記載の成型ゴムホースの製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480020445.4A CN105142870B (zh) | 2013-04-09 | 2014-04-08 | 用于制造成型橡胶软管的方法 |
JP2015511258A JP6310447B2 (ja) | 2013-04-09 | 2014-04-08 | 成型ゴムホースの製造方法 |
EP14782792.7A EP2985129B1 (en) | 2013-04-09 | 2014-04-08 | Production method for molded rubber hose |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013081120 | 2013-04-09 | ||
JP2013-081120 | 2013-04-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014168129A1 true WO2014168129A1 (ja) | 2014-10-16 |
Family
ID=51689536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/060142 WO2014168129A1 (ja) | 2013-04-09 | 2014-04-08 | 成型ゴムホースの製造方法 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2985129B1 (ja) |
JP (1) | JP6310447B2 (ja) |
CN (1) | CN105142870B (ja) |
WO (1) | WO2014168129A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112824085A (zh) * | 2019-11-20 | 2021-05-21 | 西川橡胶工业股份有限公司 | 橡胶连续硫化*** |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105599271B (zh) * | 2015-12-17 | 2019-04-09 | 天津鹏翎胶管股份有限公司 | 一种橡胶成型用实心芯轴、制备方法以及生产装置 |
CN106989219B (zh) * | 2017-04-23 | 2023-09-19 | 张东晓 | 一种膨胀胶管及其生产工艺 |
CN112265301B (zh) * | 2020-08-21 | 2022-05-10 | 成都飞机工业(集团)有限责任公司 | 一种耐高低温、高压的橡胶波纹软管的制备方法 |
US20230366490A1 (en) * | 2020-09-11 | 2023-11-16 | Parker-Hannifin Corporation | Tube assembly and method of forming same |
CN113085318B (zh) * | 2021-05-13 | 2022-12-27 | 河南理工大学 | 一种耐高温增强型橡胶组件热稳定性的物理改良方法 |
CN116690931A (zh) * | 2023-06-09 | 2023-09-05 | 东莞市裕天硅橡胶科技有限公司 | 一种气腹机用硅胶加热管的制备工艺及产品 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5919138A (ja) * | 1982-07-23 | 1984-01-31 | Sumitomo Chem Co Ltd | ゴム製品製造方法 |
JPH08157622A (ja) * | 1994-12-07 | 1996-06-18 | Bridgestone Corp | ゴムの表面処理方法 |
JP2009058010A (ja) | 2007-08-30 | 2009-03-19 | Bridgestone Corp | 外被にパ−オキサイド加硫系ゴムを用いたホ−ス及びその成型法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1080987A (fr) * | 1952-11-07 | 1954-12-15 | Continental Gummi Werke Ag | Procédé pour la fabrication de tuyaux flexibles |
EP0157956A1 (en) * | 1984-03-26 | 1985-10-16 | MATHER & PLATT LIMITED | A method of producing rubber-covered hose |
US5686505A (en) * | 1994-12-07 | 1997-11-11 | Bridgestone Corporation | Process and apparatus for surface treatment of unvulcanized rubber sheet |
JP3732638B2 (ja) * | 1997-12-28 | 2006-01-05 | 株式会社ブリヂストン | 複合曲がりホ−スの製造方法 |
CA2454491A1 (en) * | 2003-02-07 | 2004-08-07 | The Goodyear Tire & Rubber Company | Method of making curved hose |
JP2007292302A (ja) * | 2006-03-28 | 2007-11-08 | Tokai Rubber Ind Ltd | 曲り形状の樹脂複合ホース及びその製造方法 |
-
2014
- 2014-04-08 WO PCT/JP2014/060142 patent/WO2014168129A1/ja active Application Filing
- 2014-04-08 JP JP2015511258A patent/JP6310447B2/ja active Active
- 2014-04-08 CN CN201480020445.4A patent/CN105142870B/zh active Active
- 2014-04-08 EP EP14782792.7A patent/EP2985129B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5919138A (ja) * | 1982-07-23 | 1984-01-31 | Sumitomo Chem Co Ltd | ゴム製品製造方法 |
JPH08157622A (ja) * | 1994-12-07 | 1996-06-18 | Bridgestone Corp | ゴムの表面処理方法 |
JP2009058010A (ja) | 2007-08-30 | 2009-03-19 | Bridgestone Corp | 外被にパ−オキサイド加硫系ゴムを用いたホ−ス及びその成型法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112824085A (zh) * | 2019-11-20 | 2021-05-21 | 西川橡胶工业股份有限公司 | 橡胶连续硫化*** |
Also Published As
Publication number | Publication date |
---|---|
JP6310447B2 (ja) | 2018-04-11 |
CN105142870B (zh) | 2017-03-22 |
JPWO2014168129A1 (ja) | 2017-02-16 |
CN105142870A (zh) | 2015-12-09 |
EP2985129B1 (en) | 2017-09-06 |
EP2985129A4 (en) | 2016-04-20 |
EP2985129A1 (en) | 2016-02-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6310447B2 (ja) | 成型ゴムホースの製造方法 | |
JP2017007283A (ja) | 摩擦伝動ベルトの製造方法 | |
JP4871805B2 (ja) | 曲がりホース成型用金型及びこれを用いた曲がりホースの製造方法 | |
JP2008188952A (ja) | ゴムホースの製法 | |
JP2008137359A (ja) | 樹脂−ゴム複合曲がりホース成型金型および成型方法 | |
JP2019138312A (ja) | 高圧ホースの製造方法 | |
US20020096251A1 (en) | Apparatus and method for continuously and endlessly vulcanizing rubber hose | |
JP4428600B2 (ja) | 成型ホースの製造方法 | |
JP5252774B2 (ja) | アクリル系ゴム材料及び成型ホース | |
JP4131646B2 (ja) | ゴム2段加硫方法 | |
US3028276A (en) | Method of making a reinforced flexible hose having internal and external corrugations | |
JP2018052054A (ja) | ホースの製造方法 | |
JP4069141B2 (ja) | 樹脂−ゴム複合曲がりホースの製造方法 | |
EP1153733B1 (en) | Method of manufacturing curved hose | |
JP4280280B2 (ja) | 曲がりホース成型用マンドレル | |
JP4069140B2 (ja) | 樹脂−ゴム複合曲がりホースの製造方法 | |
JP2018083301A (ja) | 樹脂−ゴム複合曲がりホースの製造方法 | |
JP2009058010A (ja) | 外被にパ−オキサイド加硫系ゴムを用いたホ−ス及びその成型法 | |
JP2005014233A (ja) | ゴムホースおよびその製造方法 | |
JP5117780B2 (ja) | ゴム成形物の製造方法 | |
JP2006175602A (ja) | 繊維補強ゴム成形体の製造方法 | |
CN107849311A (zh) | 橡胶组合物、橡胶组合物金属层叠体及硫化橡胶制品 | |
JPS61206632A (ja) | 湾曲ホ−スの製造方法 | |
JPH05200854A (ja) | 成形ホースの製造方法 | |
JP2015104829A (ja) | インナーライナーのストリップワインド成形装置と成形方法および空気入りタイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480020445.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14782792 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015511258 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014782792 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014782792 Country of ref document: EP |