WO2016017765A1 - Dispositif de chauffage élastomère - Google Patents

Dispositif de chauffage élastomère Download PDF

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Publication number
WO2016017765A1
WO2016017765A1 PCT/JP2015/071672 JP2015071672W WO2016017765A1 WO 2016017765 A1 WO2016017765 A1 WO 2016017765A1 JP 2015071672 W JP2015071672 W JP 2015071672W WO 2016017765 A1 WO2016017765 A1 WO 2016017765A1
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Prior art keywords
elastomer
heater
heat generating
carbon black
elastomer composition
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PCT/JP2015/071672
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English (en)
Japanese (ja)
Inventor
泰宏 ▲高▼野
野中　敬三
奥野　茂樹
徹 野口
Original Assignee
バンドー化学株式会社
国立大学法人信州大学
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Publication of WO2016017765A1 publication Critical patent/WO2016017765A1/fr

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    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H05B3/36—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs heating conductor embedded in insulating material

Definitions

  • the present invention relates to an elastomer heater.
  • Patent Document 1 discloses a rubber sheet or a resin sheet in which a metal heating element such as a nichrome wire is embedded (see, for example, Patent Document 1). Recently, it has been proposed to use a nonmetallic conductor instead of the metal heating element.
  • Patent Document 2 discloses a polymer material having crystallinity such as polyethylene, polyethylene-vinyl acetate copolymer, polyethylene-ethyl acrylate copolymer, polyvinylidene fluoride, and carbon-based conductive materials such as carbon black, graphite, and graphite.
  • a planar heating element including a resistor formed of a mixture.
  • Patent Document 3 proposes a heating element containing fine carbon fibers such as vapor-grown carbon fibers, carbon nanofibers, and carbon nanotubes, and a resin material, and having an interelectrode resistance ( ⁇ / cm) of 10 5 or less. Yes.
  • a planar heating element in which a metal heating element as described in Patent Document 1 is embedded is inferior in flexibility and flexibility, has a low degree of freedom in deformation, and may break the metal heating element. It was difficult to use by deforming to the shape of.
  • a planar heating element manufactured using a conductive composition in which a carbon-based conductive material such as carbon black is mixed with a polymer material as described in Patent Document 2 is a planar heating element in which a nichrome wire or the like is embedded. Compared with the body, there was a problem that the electrical resistance was high and the variation in electrical resistance was large. On the other hand, in a planar heating element using a conductive composition containing a carbon-based conductive material such as carbon black, in order to reduce electrical resistance or to reduce variation in electrical resistance for each heating element, It is conceivable to increase the amount of carbon-based conductive material such as carbon black.
  • a planar heating element prepared by blending fine carbon fibers such as carbon nanotubes with a resin material as described in Patent Document 3 was prepared by blending carbon black having the same weight concentration with the resin component. The electric resistance can be lowered as compared with the planar heating element. This is because carbon nanotubes are more conductive than carbon black. On the other hand, carbon nanotubes are expensive, and it has been difficult to provide a sheet heating element using carbon nanotubes instead of carbon black at low cost. Further, it has been clarified by the present inventors that a planar heating element using carbon nanotubes may cause problems in terms of stability over time.
  • the present invention has been made in view of such problems, and an object of the present invention is an elastomer heater excellent in flexibility and flexibility, and there is little variation in heat generation between the elastomer heaters, and heat generation. It is an object of the present invention to provide an elastomer heater provided with a heat generating main body (planar heat generating element) with little change over time.
  • being excellent in flexibility means being easily deformed into an arbitrary shape.
  • the elastomer heater of the present invention is an elastomer heater comprising an electrode member and a sheet-like heat generating body using an elastomer composition containing an elastomer, conductive carbon black, and carbon nanotubes,
  • the compounding amount of the carbon nanotube in the elastomer composition is 2 to 30 parts by weight with respect to 100 parts by weight of the elastomer.
  • the elastomer heater of the present invention includes a heat generating body, and the heat generating body uses an elastomer composition containing an elastomer, conductive carbon black, and carbon nanotubes.
  • the elastomer composition contains a specific amount of carbon nanotubes together with the elastomer and conductive carbon black.
  • the elastomer composition contains carbon nanotubes together with the elastomer and the conductive carbon black.
  • the present inventors have found that the following unexpected effects can be obtained by mixing carbon nanotubes with conductive carbon black and an elastomer. That is, the present inventors have difficulty in processing an elastomer composition in which carbon nanotubes are further added to an elastomer and conductive carbon black into a sheet shape with an elastomer composition containing the elastomer and conductive carbon black. It has been found that even when conductive carbon black is contained in an amount corresponding to such a blending amount, it can be processed into a sheet shape.
  • the elastomer heater according to the present invention is an elastomer heater having excellent performance in that it has excellent flexibility and flexibility, and has little variation in heat generation for each elastomer heater.
  • the carbon nanotube is preferably a multi-wall carbon nanotube having a fiber diameter of 20 nm or less.
  • the elastomer composition is preferably prepared using a carbon nanotube masterbatch produced by an elastic kneading method.
  • the thickness of the heat generating body is preferably 0.1 to 1 mm.
  • the elastomer heater according to the present invention includes a heat generating body made of a specific elastomer composition. Therefore, the elastomer heater is an elastomer heater having a heat generating body (planar heat generating element) that is excellent in flexibility and flexibility, has little variation in heat generation between the elastomer heaters, and has little change in heat generation over time. is there.
  • a heat generating body planar heat generating element
  • FIG. 1 It is a perspective view which shows typically an example of the elastomer heater of this invention.
  • (A), (b) is a perspective view which shows typically another example of the elastomer heater of this invention, respectively.
  • (A), (b) is a perspective view which shows typically another example of the elastomer heater of this invention.
  • FIG. 1 is a cross-sectional view schematically showing an example of the elastomer heater of the present invention.
  • An elastomer heater 10 shown in FIG. 1 includes a sheet-like rectangular heat generating body 11 in plan view and two electrode bodies 12a and 12b.
  • the electrode bodies 12a and 12b are respectively long sides facing the heat generating body 11. It is buried in the vicinity.
  • a voltage is applied between the electrode bodies 12 a and 12 b and the heat generating body 11 is energized to generate heat.
  • the heat generating body 11 is made of an elastomer composition containing an elastomer, conductive carbon black, and carbon nanotubes.
  • elastomer composition containing an elastomer, conductive carbon black, and carbon nanotubes.
  • conductive carbon black and carbon nanotubes are dispersed in the elastomer. Therefore, the heat generating body 11 has conductivity, and generates heat when a voltage is applied between the electrode bodies 12a and 12b.
  • the elastomer may be a cross-linked elastomer or a thermoplastic elastomer.
  • the elastomer to be used may be appropriately selected in consideration of the heat generation temperature of the heat generating body during use. Specifically, for example, when the heat generating body generates heat at a high temperature exceeding 100 ° C., examples of the elastomer include chlorosulfonated polyethylene (CSM), ethylene / propylene rubber (EPR or EPDM), and hydrogenated nitrile rubber.
  • Cross-linked elastomers such as (H-NBR), silicone rubber and fluororubber are preferred. This is because these cross-linked elastomers hardly undergo permanent deformation even at high temperatures and have excellent heat resistance.
  • the elastomer composition contains a crosslinking agent. Therefore, when the elastomer composition contains a cross-linked elastomer and a cross-linking agent, the exothermic body is made of a cross-linked product of the elastomer composition.
  • a conventionally known crosslinking agent can be used as the crosslinking agent.
  • Specific examples of the crosslinking agent include organic peroxides and sulfur vulcanizing agents. Among these crosslinking agents, organic peroxides are preferred because their physical properties are not easily lowered by crosslinking and are excellent in heat resistance after crosslinking.
  • organic peroxide examples include dialkyl peroxides such as dicumyl peroxide, peroxyesters such as t-butyl peroxyacetate, ketone peroxides such as dicyclohexanone peroxide, and the like.
  • the amount of the organic peroxide is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the crosslinked elastomer.
  • the said elastomer composition may contain a co-crosslinking agent further as needed.
  • the crosslinking agent is an organic peroxide
  • the elastomer composition preferably contains a co-crosslinking agent.
  • a certain degree of crosslinking density is required.
  • the crosslinking density can be increased by increasing the amount of the crosslinking agent.
  • the amount of the crosslinking agent organic peroxide
  • the elongation at break of the crosslinked elastomer is lowered, and the tear strength and the like are lowered.
  • a co-crosslinking agent together with the crosslinking agent it is possible to maintain a relatively high elongation at break and tear strength while increasing the crosslinking density of the crosslinked elastomer. Therefore, by using a co-crosslinking agent together with the crosslinking agent, the bending durability of the crosslinked elastomer can be improved.
  • co-crosslinking agent examples include trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, triallyl isocyanurate, liquid polybutadiene, N, N′-m-phenylenebismaleimide, ⁇ - ⁇ such as zinc acrylate and zinc methacrylate. and metal salts of ⁇ -unsaturated organic acids. These may be used alone or in combination of two or more.
  • the amount of the co-crosslinking agent is preferably 1 to 10 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the elastomer.
  • the conductive carbon black is not particularly limited, and examples thereof include ketjen black, acetylene black, furnace black, channel black, and thermal black. These conductive carbon blacks may be used alone or in combination of two or more. Among these, ketjen black and acetylene black are preferable and ketjen black is more preferable from the viewpoint of excellent conductivity.
  • the conductive carbon black preferably has a primary particle size of 40 nm or less. This is because the conductive carbon black having a primary particle diameter of 40 nm or less is particularly suitable for imparting sufficient conductivity to the heat generating body.
  • the lower limit of the primary particle diameter of the conductive carbon black is not particularly limited, but is usually about 10 nm.
  • conductive carbon blacks having different primary particle diameters may be used in combination, and conductive carbon black having a primary particle diameter of 40 nm or less and conductive having a primary particle diameter exceeding 40 nm. The carbon black may be used in combination.
  • the primary particle size of conductive carbon black refers to observation of small spherical particles (components having a fine crystal outline and cannot be separated) constituting an aggregate of conductive carbon black by observation with an electron micrograph. For each particle in the image, an interval between two parallel lines in a fixed direction sandwiching the particle is measured as a particle diameter (Ferret diameter / Feret diameter), and an arithmetic average value obtained from the measured value.
  • Ketjen Black EC300J Ketjen Black EC600JD (all manufactured by Lion)
  • Toka Black # 5500 All manufactured by Toka Black # 4500 (all manufactured by Tokai Carbon Co.)
  • Denka Black electrochemical Manufactured by Kogyo Co., Ltd.
  • the blending amount of the conductive carbon black in the elastomer composition may be appropriately selected in consideration of the volume resistivity required for the heat generating body on the premise that it can be processed into a sheet shape. Therefore, the upper limit of the blending amount of the conductive carbon black is a limit amount at which the elastomer composition can be processed into a sheet shape. Whether or not the elastomer composition can be processed into a sheet can be determined using, for example, Mooney viscosity as an index. When the Mooney viscosity is determined as an index, the value of Mooney viscosity MS (1 + 4) 100 ° C. of the elastomer composition is preferably 200 or less.
  • the value of the Mooney viscosity MS (1 + 4) 100 ° C. is more preferably 180 or less from the viewpoint that good workability can be ensured more reliably.
  • the value of the Mooney viscosity MS (1 + 4) 100 ° C. can be measured by, for example, a Mooney viscometer MVM11 manufactured by M & K Corporation.
  • the lower limit of the Mooney viscosity MS (1 + 4) 100 ° C. is not particularly limited, and is about 10.
  • the blending amount of conductive carbon black in the elastomer composition varies depending on the type of conductive carbon black. Specifically, for example, when the conductive carbon black is Ketjen Black EC300J, the conductive carbon black is mixed. The amount of the functional carbon black is preferably about 30 to 100 parts by weight with respect to 100 parts by weight of the elastomer. For example, when the conductive carbon black is Ketjen Black EC600JD, the blending amount of the conductive carbon black is preferably about 10 to 45 parts by weight with respect to 100 parts by weight of the elastomer. Further, for example, when the conductive carbon black is Talker Black # 5500, the blending amount of the conductive carbon black is preferably about 50 to 120 parts by weight with respect to 100 parts by weight of the elastomer.
  • the elastomer composition contains carbon nanotubes together with conductive carbon black.
  • the present invention achieves both excellent processability and high conductivity, which has been difficult to achieve with only conductive carbon black.
  • the carbon nanotubes may be single-walled carbon nanotubes (SWCNT) or multi-walled carbon nanotubes (MWCNT).
  • SWCNT single-walled carbon nanotubes
  • MWCNT multi-walled carbon nanotubes
  • the carbon nanotube is preferably a multi-walled carbon nanotube because it can be procured at a low cost.
  • the carbon nanotube may be a commercial product.
  • the fiber diameter of the carbon nanotube is preferably 20 nm or less. This is because it is suitable for improving the processability of the elastomer composition and reducing the volume resistivity of the heat generating body.
  • the fiber diameter of the carbon nanotube is more preferably 15 nm or less.
  • the compounding amount of the carbon nanotube is 2 to 30 parts by weight with respect to 100 parts by weight of the elastomer.
  • the compounding amount of the carbon nanotubes exceeds 30 parts by weight, the volume specific resistance of the heat generating body using the elastomer composition increases remarkably with time.
  • the compounding amount of the carbon nanotube is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the elastomer.
  • the elastomer composition may further contain a vulcanization accelerator, an anti-aging agent, a plasticizer, a processing aid, a stabilizer and the like as necessary. Each of these various additives may be used alone or in combination of two or more.
  • the vulcanization accelerator is used together with a sulfur vulcanizing agent. Specific examples of the vulcanization accelerator include, for example, thiuram-based, sulfenamide-based, dithiocarbamate-based, guanidine-based, and thiocrea-based vulcanization accelerators.
  • the blending amount of the vulcanization accelerator is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the elastomer.
  • anti-aging agent examples include diamine-based anti-aging agents and phenol-based anti-aging agents.
  • the blending amount of the anti-aging agent is preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the elastomer.
  • plasticizer examples include dialkyl phthalates such as dibutyl phthalate (DBP) and dioctyl phthalate (DOP), dialkyl adipates such as dioctyl adipate (DOA), and dialkyl sebacates such as dioctyl sebacate (DOS).
  • the blending amount of the plasticizer is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the elastomer.
  • process oil can be used as the processing aid.
  • the process oil include paraffinic process oil, naphthenic process oil, aromatic process oil, and fluorine process oil.
  • the amount of the processing aid is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the elastomer. Further, when the elastomer is a fluoro rubber, it is preferable to use a fluoro process oil as a processing aid.
  • the volume specific resistance of the heat generating body using such an elastomer composition is not particularly limited, but is preferably 1.0 ⁇ ⁇ cm or less.
  • the volume resistivity is 1.0 ⁇ ⁇ cm or less, not only when using a high voltage power supply such as 120 V or 240 V, but also when using a low voltage power supply such as 12 V, heat is easily generated to a practical temperature. Can be made. Further, even when a low voltage power source such as 12V is used, the distance between the electrodes can be increased, which is advantageous in obtaining a large-area heating element.
  • the volume resistivity is in the above range, it is advantageous when designing the heat generating body to be thin.
  • the elastomer heater of the present invention may use a high voltage power source such as 120V or 240V as a power source.
  • a high voltage power source such as 120V or 240V
  • the volume resistivity of the heat generating body does not have to be as low as 1.0 ⁇ ⁇ cm or less, and even a volume resistivity exceeding 1.0 ⁇ ⁇ cm can generate heat up to a practical temperature, Exothermic.
  • the elastomer heater of the present invention even when a high voltage is applied to heat the heat generating body, the effect of the heat generating body containing a specific amount of carbon nanotubes together with the elastomer and the conductive carbon black, that is, heat generation It is possible to enjoy the effect that there is little variation in heat resistance and that the exothermic change with time is small.
  • the heat generating body preferably has a thickness of 0.1 to 1.0 mm. If the thickness of the heat generating body is less than 0.1 mm, the durability may be insufficient. On the other hand, if the thickness of the heat generating main body exceeds 1.0 mm, the heat generating main body is inferior in flexibility and free deformation may be hindered.
  • a protective layer may be laminated on the front surface and / or the back surface of the heat generating body.
  • the protective layer for example, a layer made of a composition containing the same composition as the elastomer composition, except that it does not contain conductive carbon black and carbon nanotubes, or a layer made of an insulating resin film Is mentioned.
  • the heat generating body can have only the surface opposite to the side on which the foam film is laminated as the heat generating surface.
  • the other layer may be an adhesive layer or a pressure-sensitive adhesive layer for attaching the elastomer heater to another member.
  • the electrode bodies 12a and 12b are not particularly limited as long as they are made of a conductive material and have flexibility.
  • the electrode main body include a flat string formed by knitting a copper wire such as a flat knitted tin-plated copper wire, a net-like material made of nickel foil, copper wire or conductive fiber.
  • a flat string-like electrode such as a flat knitted tin-plated copper wire is preferable because the thickness of the electrode body can be reduced and the bending fatigue resistance is excellent.
  • the size of each member is not particularly limited, and may be appropriately selected in consideration of the required amount of heat generation.
  • the heater capacity (W) indicating the heat generation capability of the elastomer heater is a product of voltage and current.
  • the elastomer heater of the present invention is not limited to the one having the configuration shown in FIG. 1, and may have, for example, the configuration shown in FIG.
  • FIGS. 2A and 2B are perspective views schematically showing another example of the elastomer heater of the present invention.
  • the elastomer heater 20 shown in FIG. 2A includes a sheet-like heat generating body 21 having a rectangular shape in plan view, and three electrode bodies 22a, 22b, and 22c.
  • the electrode bodies 22a, 22b, and 22c include the heat generating body 21. It is embedded at substantially equal intervals, almost parallel to the long side of.
  • a voltage is applied between the electrode bodies 22a and 22b and between the electrode bodies 22b and 22c (for example, a voltage is applied using the electrode bodies 22a and 22c as a positive electrode and the electrode body 22b as a negative electrode), By energizing the heat generating main body 21, the heat generating main body 21 is caused to generate heat.
  • the elastomer heater 30 shown in FIG. 2 (b) includes a sheet-like heat generating body 31 that is rectangular in plan view and five electrode bodies 32a to 32e.
  • the electrode bodies 32a to 32e are connected to the long sides of the heat generating body 31. They are buried almost parallel and at almost equal intervals.
  • a voltage is applied between the electrode bodies 32a and 32b, between the electrode bodies 32b and 32c, between the electrode bodies 32c and 32d, and between the electrode bodies 32d and 32e (for example, the electrode bodies 32a, 32c and 32e are connected).
  • a voltage is applied using the plus electrode and the electrode bodies 32b and 32d as a minus electrode), and the heat generating body 31 is energized by energizing the heat generating body 31.
  • the elastomer heater of the present invention may include three or more electrode bodies.
  • the elastomer heater of the present invention can adjust the distance between the electrode bodies by increasing or decreasing the number of the electrode bodies with respect to the heat generating body having the same shape, and thereby the amount of heat generated by the heat generating body. Can be adjusted.
  • the distance between the electrode bodies does not necessarily have to be equal.
  • the heat generation temperature is set to a different temperature for each region sandwiched between the electrode bodies while using the same power source. Can do.
  • the elastomer heater of the present invention is an elastomer heater provided with three or more electrode bodies as shown in FIGS. 2 (a) and 2 (b), the two outer electrode bodies (FIG. 2 ( The electrode bodies 22a and 22c in a) and the electrode bodies 32a and 32e) in FIG. 2B are preferably homopolar electrode bodies.
  • the elastomer heater having such a configuration is not short-circuited even when the two outermost electrode bodies are in contact with each other when the elastomer heater is spirally wound around a columnar member. It is.
  • the elastomer heater of the present invention may have the configuration shown in FIG. 3 (a) and 3 (b) are perspective views schematically showing another example of the elastomer heater of the present invention.
  • the elastomer heater 40 shown in FIG. 3A has the same configuration as the elastomer heater 10 shown in FIG. 1, and a plurality of slits 43 parallel to each other are formed in the heat generating body 41.
  • the slit 43 is formed over the entire area between the electrode bodies 42a and 42b in a direction substantially perpendicular to the electrode bodies 42a and 42b. Since the elastomer heater 40 is formed with such a slit 43, the heat generating body 41 (elastomer heater 40) can be more freely deformed.
  • the elastomer heater 40 in which the slits 43 are formed in the heat generating body 41 can be easily used by being attached to a curved surface, for example.
  • each of the plurality of slits 53 may be formed only on a part of the heat generating body 51 in a direction substantially perpendicular to the electrode bodies 52a and 52b.
  • the position and number of the slit are not limited at all and are arbitrary.
  • the slits may be formed in an appropriate number at an appropriate position in consideration of the deformation mode of the elastomer heater.
  • the slit may be formed so as to penetrate the heat generating body in the thickness direction, or may be formed only in a part of the heat generating body in the thickness direction.
  • an elastomer composition is prepared.
  • the elastomer composition may be prepared by adding all of the elastomer, conductive carbon black and carbon nanotubes, and optional components to be added as necessary to a Banbury mixer or the like and kneading them in one step.
  • the elastomer composition is prepared by previously kneading an elastomer and carbon nanotubes by an elastic kneading method to prepare a master batch of carbon nanotubes, and then kneading the obtained master batch and other components. It is preferable to prepare in the process.
  • each component can be uniformly dispersed in the elastomer, and particularly bulky conductive carbon black and carbon nanotubes can be uniformly dispersed in the elastomer. Also, by using this method, the carbon nanotubes can be defibrated and dispersed.
  • the elastic kneading method for preparing the carbon nanotube master batch can be carried out, for example, by the following methods (A) to (C).
  • the kneaded product obtained in the second kneading step is passed through a roll having a roll gap of about 0.3 mm at a temperature of 0 to 50 ° C. several times (for example, 10 The third kneading step is repeated.
  • the third kneading step is preferably performed using an open roll.
  • the first kneading step and the second kneading step may be performed using an open roll, and each kneading step is performed using a twin screw extruder or the like. May be.
  • kneading conditions kneading time, rotor gap, rotor rotational speed, etc.
  • carbon nanofibers can be dispersed throughout the elastomer by a high shearing force by performing the first kneading step, and the carbon nanofibers are aggregated by radicals of the elastomer molecules by performing the second kneading step. You can unravel the lumps.
  • the elastomer in which radicals are generated acts so as to pull out the carbon nanofibers one by one, and the carbon nanofibers can be further dispersed. Therefore, in the elastic kneading method, a master batch of carbon nanotubes in which the carbon nanotubes are defibrated and uniformly dispersed in the elastomer can be prepared.
  • the masterbatch After preparing the masterbatch, the masterbatch, elastomer, conductive carbon black, and other optional components, Banbury mixer, kneader, open roll, etc. Use to knead. Thereby, an elastomer composition can be prepared.
  • the elastomer composition is processed into a sheet to produce a sheet of the elastomer composition.
  • the elastomer composition may be processed by a conventionally known method such as roll processing or calendar processing.
  • the processing temperature when processing the elastomer composition is, for example, about 20 to 120 ° C.
  • an electrode main body is integrated with the sheet-like material produced at the process of said (2), and an elastomer heater is completed.
  • the sheet-like material and the electrode body may be integrated by, for example, the following method (3-1) or the method (3-2) below. (3-1) Two sheets of the sheet-like material are produced, the electrode body is sandwiched between the two sheet-like objects at a predetermined position, and the laminate of the sheet-like material and the electrode body is used for press molding. The sheet-like material and the electrode body are integrated by putting them into the mold, pressurizing and heating.
  • an elastomer composition containing a crosslinked elastomer and a crosslinking agent is used as the elastomer composition, an uncrosslinked sheet is vulcanized and the electrode body is vulcanized and bonded to the heat generating body.
  • an adhesive may be applied to the surface of the electrode body before the electrode body is integrated with the sheet. Thereby, joining of the said electrode main body and the said heat-generation main body can be strengthened more.
  • the adhesive does not inhibit conduction between the electrode bodies as an insulating layer.
  • the adhesive is applied only to a part of the electrode body, the adhesive is thinly applied, and the elastomer composition which is a conductor diffuses to the electrode side during press molding, and the electrode It is possible to adopt measures such as using a conductive adhesive as an adhesive.
  • the elastomer heater of the present invention can be used for various applications as a planar heating element. Specifically, for example, for various applications such as handle heaters for motorcycles and automobiles, heaters for floors and seats, snow melting devices installed on the roofs of roads and houses, heat-retaining devices for foods, warmers, etc. Can be used. Since the elastomer of the present invention is excellent in flexibility and flexibility, it is suitable for being used by being affixed to a curved surface or in a form that is deformed during use.
  • Elastomer ethylene propylene rubber
  • EP123 (manufactured by JSR)
  • Conductive carbon black Ketjen Black EC300J (Lion Corporation)
  • Conductive carbon black Ketjen black EC600JD (manufactured by Lion)
  • Conductive carbon black Toka Black # 5500 (manufactured by Tokai Carbon Co., Ltd.)
  • Carbon nanotube Nanosil NC7000 (fiber diameter 9.5 nm, average length 1.5 ⁇ m, aspect ratio 158, carbon purity 90%) (manufactured by Nanosil (Belgium))
  • Carbon nanotube Flotube 9000 (fiber diameter 10 to 15 nm, average length 10 ⁇ m, carbon purity 95.0 to 97.5%) (manufactured by CNano (USA))
  • Graphite Earth-like graphite powder AP (manufactured by Nippon Graphite Industry Co., Ltd.)
  • Process oil Thumper 2280 (manufactured by N
  • the mixture is discharged from the Banbury mixer, the mixture is cooled to room temperature (25 ° C.), set to a roll gap of 0.3 mm using an open roll through which cooling water is passed, and the mixture is passed through 3 times. went. Finally, it was processed into a sheet shape with a roll gap of 1 mm to obtain a sheet-shaped master batch.
  • the obtained elastomer composition was processed into a sheet using a 10-inch roll (roll temperature 80 ° C), and an unvulcanized rubber sheet having a thickness of 0.4 mm. (Uncrosslinked elastomer sheet) was produced. Thereafter, the unvulcanized rubber sheet was cut to produce two unvulcanized rubber sheets of a predetermined size.
  • the sizes of the unvulcanized rubber sheets were as follows: the unvulcanized rubber sheets of Examples 1 to 13 and Comparative Examples 1 to 9 were 86 mm wide ⁇ 100 mm long, and Examples 14 to 19 and Comparative Examples 10 to 10 were used. The size of 12 unvulcanized rubber sheets was 306 mm wide ⁇ 100 mm long.
  • two electrode bodies were arranged as follows. That is, in Examples 1 to 13 and Comparative Examples 1 to 9, the distance between the electrode bodies is 80 mm parallel to the long side of the unvulcanized rubber sheet, and the end of the electrode body is 20 mm from the unvulcanized rubber sheet. Arranged in the vicinity of each of the two long sides of the unvulcanized rubber sheet so as to protrude. In Examples 14 to 19 and Comparative Examples 10 to 12, the distance between the electrode bodies was 300 mm parallel to the short side of the unvulcanized rubber sheet, and the end of the electrode body was 20 mm from the unvulcanized rubber sheet. Arranged in the vicinity of each of the two short sides of the unvulcanized rubber sheet so as to protrude. In each example and comparative example, ten elastomer heaters were produced by the method described above.
  • the elastomer heaters produced in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 3 and 4. The following evaluations 2 to 4 were performed with 10 samples. The evaluations 2 and 3 below were performed using an elastomer heater stored at room temperature for 1 day after production.
  • A Cracks did not occur in the elastomer composition wound around the roll, and the sheets could be taken out continuously.
  • D Many cracks of 2 cm or more were confirmed in the whole elastomer composition wound around the roll, and the sheet could not be pulled out continuously.
  • volume Specific Resistance A DC voltage of 12 V was applied between the electrode bodies of the produced elastomer heater, the current value flowing through the heat generating body at that time was measured, the resistance value was calculated, and the volume specific resistance ( ⁇ ⁇ cm) was obtained. The volume specific resistance was calculated as an average value of 10 samples.
  • Heat generation temperature A DC voltage was applied between the electrode bodies of the produced elastomer heater to heat the electrode body, and the temperature was measured. At this time, the applied DC voltage was 12 V in Examples 1 to 13 and Comparative Examples 1 to 9, 240 V in Examples 14 to 16 and Comparative Examples 10 and 11, and 120 V in Examples 17 to 19 and Comparative Example 12. .
  • the exothermic temperature was measured using an infrared thermography (TVS-200) manufactured by Nippon Avionics. At this time, the temperature of arbitrary 5 places in the heat generating body was measured, and the average value was defined as the heat generating temperature.
  • ⁇ T (° C.) was calculated as a difference between an exothermic temperature at the start of voltage application and an exothermic temperature after 120 seconds from the voltage application.
  • the temperature difference was calculated for each of the 10 samples, and the average value was used as the evaluation result.
  • Rate of change in volume resistivity (%) [((volume resistivity after 30 days from production) ⁇ (volume resistivity after 1 day of production)) / (volume resistivity after 1 day of production)] ⁇ 100
  • a heat generating body was prepared using an elastomer composition in which 2 to 30 parts by weight of carbon nanotubes were blended with 100 parts by weight of elastomer in addition to elastomer and conductive carbon black.
  • the elastomer composition was excellent in roll processability, the variation in heat generation temperature for each elastomer heater was small, and the variation in volume resistivity with the passage of time was also small.
  • carbon nanotubes are not blended in the elastomer composition, or even if blended, the amount is less than 2 parts by weight with respect to 100 parts by weight of the elastomer, and conductive carbon black is blended.
  • the amount was increased, the processability of the elastomer composition was extremely poor, and the produced elastomer heater had a large variation in heat generation temperature for each elastomer heater (Comparative Examples 1, 2, 4, 6, 11). 12).
  • carbon nanotubes exceeding 30 parts by weight with respect to 100 parts by weight of the elastomer are blended, or conductive carbon black is not blended in the elastomer composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Resistance Heating (AREA)

Abstract

L'objectif de la présente invention est de pourvoir à un dispositif de chauffage élastomère qui est souple et cintrable et qui est équipé d'un corps principal de chauffage à faible variation des propriétés de chauffage et faible changement au cours du temps des propriétés de chauffage. Ce dispositif de chauffage élastomère est équipé d'un élément d'électrode et d'un corps principal de chauffage en forme de feuille formé à l'aide d'une composition élastomère qui contient un élastomère, du noir de carbone conducteur et des nanotubes de carbone, la quantité du noir de carbone dans la composition élastomère étant comprise entre 2 et 30 parties en poids par rapport à 100 parties en poids de l'élastomère.
PCT/JP2015/071672 2014-07-31 2015-07-30 Dispositif de chauffage élastomère WO2016017765A1 (fr)

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JP6174220B1 (ja) * 2016-10-07 2017-08-02 イシイ株式会社 面状発熱体、面状発熱装置、面状発熱体用電極、及び面状発熱体の製造方法
WO2017202350A1 (fr) * 2016-05-24 2017-11-30 Advanced Materials Enterprises Co., Ltd Appareil de manipulation de température et son procédé de préparation
WO2019075173A3 (fr) * 2017-10-11 2019-06-20 General Nano Llc Couverture chauffante et procédé d'utilisation
WO2020031607A1 (fr) * 2018-08-08 2020-02-13 バンドー化学株式会社 Courroie de transmission à friction
CN111372335A (zh) * 2018-12-26 2020-07-03 弈禔股份有限公司 导电性发热材料及使用所述导电性发热材料的组件
US11021369B2 (en) 2016-02-04 2021-06-01 General Nano Llc Carbon nanotube sheet structure and method for its making
US11021368B2 (en) 2014-07-30 2021-06-01 General Nano Llc Carbon nanotube sheet structure and method for its making
JP7453081B2 (ja) 2019-08-13 2024-03-19 三ツ星ベルト株式会社 ゴム組成物ならびにその製造方法および用途

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US11021368B2 (en) 2014-07-30 2021-06-01 General Nano Llc Carbon nanotube sheet structure and method for its making
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JP6174220B1 (ja) * 2016-10-07 2017-08-02 イシイ株式会社 面状発熱体、面状発熱装置、面状発熱体用電極、及び面状発熱体の製造方法
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CN111372335A (zh) * 2018-12-26 2020-07-03 弈禔股份有限公司 导电性发热材料及使用所述导电性发热材料的组件
JP7453081B2 (ja) 2019-08-13 2024-03-19 三ツ星ベルト株式会社 ゴム組成物ならびにその製造方法および用途

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