WO2023188956A1 - Élément chauffant en forme de feuille et adhésif à base de fluor utilisé dans ce dernier - Google Patents

Élément chauffant en forme de feuille et adhésif à base de fluor utilisé dans ce dernier Download PDF

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Publication number
WO2023188956A1
WO2023188956A1 PCT/JP2023/005506 JP2023005506W WO2023188956A1 WO 2023188956 A1 WO2023188956 A1 WO 2023188956A1 JP 2023005506 W JP2023005506 W JP 2023005506W WO 2023188956 A1 WO2023188956 A1 WO 2023188956A1
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Prior art keywords
sheet
layer
adhesive layer
adhesive
fluorine
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PCT/JP2023/005506
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English (en)
Japanese (ja)
Inventor
匠 深澤
誠 後藤
卓 蔵原
陽輔 菅原
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株式会社巴川製紙所
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Publication of WO2023188956A1 publication Critical patent/WO2023188956A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/04—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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 a sheet heater and a fluorine-based adhesive used therein.
  • Patent Document 1 discloses a sheet-like heating element in which a lead wire is connected to a terminal portion connected to a conductive heating element, and at least one entire surface of the conductive heating element, or the conductive heating element and the terminal portion.
  • a low thermal expansion resin layer having a coefficient of thermal expansion of 8 x 10 -5 °C or less is provided on at least one entire surface of the sheet-like heating element containing the heating element, and the layer is sandwiched from both sides by fluororesin layers A that can be heat-sealed to each other.
  • a heat diffusion material layer is provided on each surface of the double-sided heat-sealable fluororesin layer A, and another heat-sealable fluorine resin layer is further provided on the surface of this heat-sealable material layer.
  • a planar heater including a resin layer B is described. According to such a planar heater of the present invention, since it has a heat diffusion material layer, even if the conductive heating element is extremely thin, the heat fusion process by heating the resin at the time of manufacturing can be easily performed. At times, the deforming force due to resin contraction is suppressed by the heat diffusion material layer that is crimped with the resin, so it is not transmitted to the conductive heating element itself, and as a result, the sheet heater deforms into a wave shape.
  • the heater does not bend or warp, it can be made into an accurately flat sheet heater. Therefore, it is stated that it can be made into a stable and constant shape, and that even when immersed in the liquid to be heated, it is possible to reliably and completely immerse the planar heater.
  • Patent Document 2 describes a planar heating element in which an insulating outer skin is laminated and integrated on both sides of a metal resistor on which a heating circuit is formed via a heat-fusible adhesive layer, in which a heat-fusible adhesive layer is used as the heat-fusible adhesive layer.
  • a planar heating element is described in which a fluororesin is used and a glass cloth impregnated with polytetrafluoroethylene (hereinafter referred to as "PTFE”) and sintered is used as the insulating outer skin.
  • PTFE polytetrafluoroethylene
  • a PFA film or FEP film is interposed between PTFE-impregnated glass cloth as a heat-melting adhesive layer, and a metal resistor is sandwiched and heated and pressurized to heat-fuse it, so that it can be used continuously. It is possible to obtain a planar heating element that is heat resistant to temperatures of 200°C or higher, and since PTFE-impregnated glass cloth is used as the insulating outer cover, there is no warping or other deformation due to temperature rises or falls. It is also described as having high mechanical strength.
  • Patent Document 3 discloses a planar heater including a heat generating layer and a first fluororubber layer disposed on both sides of the heat generating layer, the first fluororubber layer having a durometer type A hardness of 65 or less according to JIS K 6253. is listed. It is also described that according to such a planar heater, it is possible to provide a planar heater with improved heat conduction efficiency in a planar heater whose heat generating layer is covered with a fluororubber layer.
  • Patent Document 4 discloses that the heating element is composed of a heating element and a fluororubber sheet adhered to the heating element, and is composed of a glass cloth and a fluororubber layer impregnated with the glass cloth via an adhesive strength agent.
  • a fluororubber sheet heater is described in which the fluororubber sheet has a glass cloth and a fluororubber layer impregnated into the glass cloth with an adhesive strength enhancer. It is also described that such a fluororubber sheet heater has excellent heat resistance, cold resistance, acid resistance, oil resistance, and solvent resistance, and also excellent flexibility and impact resistance because it is a rubber elastic body.
  • the object to be heated has a curved surface such as a pipe
  • a sheet-shaped heater when installed on the curved surface, a tensile (elongation) stress load is applied to the outer circumferential side of the sheet-shaped heater.
  • the present invention provides sheet-like heaters and heaters that can reduce the tensile (elongation) stress load when placed on the curved surface of a heated object having a curved surface such as piping, and that also have high insulation properties.
  • fluorine-based adhesives used for this purpose.
  • the present inventor has made extensive studies to solve the above problems and has completed the present invention.
  • the present invention includes the following (1) to (9).
  • THF tetrahydrofuran
  • the fluorine-based adhesive is The above (1) is one in which the ratio (percentage: E 2 /E 1 ⁇ 100) of the storage elastic modulus (E 2 ) at 70°C to the storage elastic modulus (E 1 ) at 25°C is 8 to 92%. ) Fluorine-based adhesives listed in ).
  • the sheet-like heater A high-strength, high-insulation sheet whose reinforcing fibers are impregnated with fluororesin, a first adhesive layer; a first insulating layer; a second adhesive layer; a heating layer; are stacked in this order, The main surfaces of the high-strength and high-insulating sheet and the first adhesive layer are in close contact with each other, The main surfaces of the first adhesive layer and the first insulating layer are in close contact with each other, The main surfaces of the second adhesive layer and the heat generating layer are in close contact with each other, The fluorine-based adhesive according to (1) or (2) above, used as the first adhesive layer.
  • the main surfaces of the high-strength and high-insulating sheet and the first adhesive layer are in close contact with each other,
  • the main surfaces of the first adhesive layer and the first insulating layer are in close contact with each other,
  • the main surfaces of the second adhesive layer and the heat generating layer are in close contact with each other,
  • the first adhesive layer is 1000g of tetrahydrofuran (THF) was placed in a 2L polybottle, adjusted to 23°C, and stirred at 600 rpm using a medium viscosity stirrer using a disper blade with a blade diameter of 40mm as the stirring blade.
  • THF tetrahydrofuran
  • a sheet-shaped heater made of fluorine-based adhesive.
  • the fluorine-based adhesive is The above (4), in which the ratio (percentage: E 2 /E 1 ⁇ 100) of the storage elastic modulus (E 2 ) at 70°C to the storage elastic modulus (E 1 ) at 25°C is 8 to 92%.
  • Sheet-shaped heater described in . ( 6 ) The ratio (h 1 / The sheet-like heater according to (4) or (5) above, wherein H total ) is 0.10 or more.
  • the thickness of the high strength and high insulation sheet is 100 to 300 ⁇ m
  • the tensile (elongation) stress load when placed on the curved surface of an object to be heated such as a pipe, the tensile (elongation) stress load can be reduced, and in addition, the sheet-shaped material has high insulation properties.
  • a heater and a fluorine-based adhesive used therein can be provided.
  • FIG. 1 is a cross section (schematic cross-sectional view) that appears when a preferred embodiment of the heater of the present invention is cut in a direction perpendicular to its main surface.
  • tetrahydrofuran 1000 g is placed in a 2 L polyethylene bottle, the temperature is adjusted to 23°C, and this is stirred at 600 rpm using a medium viscosity stirrer using a disper blade with a blade diameter of 40 mm as a stirring blade.
  • THF tetrahydrofuran
  • a medium viscosity stirrer using a disper blade with a blade diameter of 40 mm as a stirring blade.
  • pour 1 to 50 g of a granular sample with a diameter of 0.5 to 2.0 cm into the container and check whether the entire amount has dissolved after 24 hours. If the entire amount has dissolved, pour it again.
  • the present invention provides a structure in which a high-strength, high-insulating sheet in which reinforcing fibers are impregnated with a fluororesin, a first adhesive layer, a first insulating layer, a second adhesive layer, and a heat generating layer are laminated in this order.
  • the high-strength, high-insulating sheet and the first adhesive layer have their main surfaces in close contact with each other, and the first adhesive layer and the first insulating layer have their main surfaces in close contact with each other, The main surfaces of the second adhesive layer and the heat generating layer are in close contact with each other.
  • the adhesive of the present invention will be explained.
  • the adhesive of the present invention can be preferably used for adhesion between layers in a sheet-like heater having a laminated structure.
  • a sheet-like heater having a laminated structure means a heater having a structure in which the main surfaces of each layer are in close contact with each other and each layer is laminated, like the heater of the present invention described later.
  • the adhesive of the present invention is a fluorine-based adhesive, and the solubility obtained when subjected to a solvent solubility test is 5 to 30% by mass, preferably 10 to 28% by mass.
  • the solvent solubility test refers to putting 1000g of tetrahydrofuran (THF) into a 2L polyethylene bottle, adjusting the temperature to 23°C, and stirring it at 600 rpm using a medium-viscosity stirrer using a disper blade with a blade diameter of 40mm as the stirring blade.
  • 1 to 50 g of a granular sample (adhesive of the present invention) with a diameter of 0.5 to 2.0 cm was charged into the stirring medium, and after 24 hours it was confirmed whether the entire amount had dissolved. If the entire amount has been dissolved, add 1 to 50 g of the sample (adhesive of the present invention) again, and repeat the operation to check whether it has dissolved after 24 hours. This is a test to determine the maximum amount (solubility).
  • the adhesive of the present invention preferably has a fluorine content of 64% by mass or less, more preferably 57 to 60% by mass.
  • the fluorine content contained in the adhesive of the present invention is determined by absorbing the combustion gas of fluororesin into an absorption liquid using a method based on JIS K 7217, which is a method for analyzing plastic combustion gas, and measuring the fluorine content in accordance with JIS K 0102 34.1. It means the value obtained by quantitative analysis.
  • the adhesive of the present invention is a fluorine-based adhesive, and the unsaturated bond content is preferably within the range of 0.1 to 20%, and preferably within the range of 0.1 to 10%. It is more preferable that
  • the unsaturated bond content contained in the adhesive of the present invention is determined by the peak (4.5 to 6.0 ppm) derived from unsaturated bond hydrogen in the alkyl chain in the spectrum obtained by 1 H-NMR (solid-state NMR) measurement. It is calculated from the ratio of the integrated amount of peaks derived from saturated bonded hydrogen to the integrated amount of peaks derived from saturated bonded hydrogen.
  • the adhesive of the present invention is a fluorine-based adhesive and preferably has a storage modulus (E 1 ) of 0.2 to 15 MPa at 25°C, more preferably 1 to 10 MPa. More preferred.
  • the storage elastic modulus (E 1 ) of the adhesive of the present invention at 25°C is measured using a dynamic thermoelasticity measuring device using a 400 ⁇ m thick adhesive layer, at a measurement frequency of 10Hz, and at a measurement temperature of 0°C to 120°C. Measurement is performed while increasing the temperature at 3°C/min until 25°C, and the value obtained at 25°C is taken as the value.
  • the adhesive of the present invention is a fluorine-based adhesive and preferably has a storage modulus (E 2 ) of 0.1 to 10 MPa at 70°C, preferably 0.5 to 8 MPa. It is more preferable.
  • the storage elastic modulus (E 2 ) of the adhesive of the present invention at 70°C is measured using a dynamic thermoelasticity measuring device using an adhesive layer with a thickness of 400 ⁇ m, at a measurement frequency of 10Hz, and at a measurement temperature of 0°C to 120°C. Measurement is performed while increasing the temperature at 3°C/min until 70°C, and the value obtained at 70°C is taken as the value.
  • the adhesive of the present invention is a fluorine-based adhesive, and has a ratio (percentage: E 2 / E 1 ⁇ 100) is preferably 8 to 92%, more preferably 20 to 85%.
  • the adhesive of the present invention is preferably used to form the first adhesive layer in the heater of the present invention, which will be described later.
  • a sheet-shaped heater having a laminated structure using the adhesive of the present invention for adhesion between each layer has a tensile strength when placed on a curved surface of a heated object such as a pipe. (Elongation) Stress load can be reduced.
  • the adhesive of the present invention is a fluorine-based adhesive, and the ratio of the storage elastic modulus (E 2 ) at 70°C to the storage elastic modulus (E 1 ) at 25°C (percentage: E 2 / When E 1 ⁇ 100) is 8 to 92% (preferably 20 to 85%), a sheet-like heater with a laminated structure using this for adhesion between layers can be used to heat objects with curved surfaces such as piping.
  • the present inventors have found that when placed on the curved surface of , it is easy to curl. In such a sheet-like heater, when electricity is applied to the heat generating layer, the elastic modulus of the fluorine-based adhesive decreases due to the heat emitted from the heat generating layer.
  • the fluorine-based adhesive easily follows the deformation and deforms.
  • the power supply to the heating layer is stopped while the sheet heater is kept in close contact with the curved surface of the object to be heated, and when the temperature of the sheet heater is lowered to about room temperature, the elastic modulus of the fluorine adhesive increases.
  • the sheet-like heater has a curling tendency, and as a result, the sheet-like heater can be easily placed on the curved surface of an object to be heated, such as a pipe, that has a curved surface.
  • a sheet-like heater having a laminated structure using the adhesive of the present invention for adhesion between layers is placed on a curved surface of a heated object having a curved surface such as piping, it is possible to align the heater in advance along the curved surface. If the sheet-like heater is curved, the workability of the sheet-like heater on the curved surface of the object to be heated will be improved.
  • the ratio (percentage: E 2 /E 1 ⁇ 100) of the storage elastic modulus (E 2 ) at 70°C to the storage elastic modulus (E 1 ) at 25°C is 8 to 92% (preferably 20 to 85%).
  • a sheet-like heater having a laminated structure using the adhesive of the present invention for adhesion between layers can be easily curved in advance to follow the curved surface of the heated object.
  • a method of pre-curving such a sheet-shaped heater before installation for example, a cylinder with a curved surface of the same degree of curvature as the object to be heated and the sheet-shaped heater are placed in an oven and heated to approximately 110°C. After heating and bending the cylinder by wrapping a sheet heater around the outer surface of the cylinder in an oven, take out the cylinder with the sheet heater wrapped around it from the oven and let it cool down to room temperature, then remove the sheet heater from the cylinder.
  • FIG. 1 shows a cross section that appears when a preferred embodiment of the heater of the present invention is cut in a direction perpendicular to its main surface. Since FIG. 1 is a schematic cross-sectional view, each dimension in FIG. 1 may differ from the actual size.
  • the heater 1 of the present invention shown in FIG. 13 and the second insulating layer 15 are laminated in this order, and the main surfaces of the adjacent layers are in close contact with each other. That is, in the heater of the present invention, it is not essential that the main surfaces of the first insulating layer 7 and the second adhesive layer 9 are in close contact with each other, and another layer may be included between these layers. In the preferred embodiment shown in FIG. 1, the main surfaces of the first insulating layer 7 and the second adhesive layer 9 are in close contact with each other. Similarly, in the heater of the present invention, the main surfaces of the heat generating layer 11, the third adhesive layer 13, and the second insulating layer 15 do not need to be in close contact with each other, but in the preferred embodiment shown in FIG. These layers are in close contact.
  • the heater of the present invention does not need to have the third adhesive layer and the second insulating layer, it is preferable to have these layers as in the preferred embodiment shown in FIG.
  • the high-strength, high-insulating sheet 3 is a sheet in which reinforcing fibers are impregnated with a fluororesin, and has high strength and high insulation properties.
  • the reinforcing fibers are fibers with high strength, and may be conventionally known reinforcing fibers.
  • the material for the reinforcing fibers include glass, aramid (aromatic polyamide resin), and carbon fiber.
  • the reinforcing fibers preferably have a cross-sectional diameter (equal area circle equivalent diameter) of about 5 to 10 ⁇ m. It is preferable that the reinforcing fibers are plain-woven in the form of a sheet. In other words, it is preferable that the material be in the form of a woven fabric.
  • the high-strength, high-insulating sheet 3 is made by impregnating the above-mentioned reinforcing fibers with a fluororesin.
  • the fluororesin is not particularly limited, but examples include polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer.
  • the reinforcing fibers may be primed and then impregnated with a fluororesin.
  • the high-strength, highly insulating sheet 3 is preferably a glass fiber woven fabric, that is, a glass cloth impregnated with PTFE.
  • the thickness of the high-strength, highly insulating sheet is not limited, but is preferably 100 to 300 ⁇ m, more preferably 125 to 200 ⁇ m.
  • the thickness of the high-strength, high-insulating sheet shall mean the value obtained by measuring as follows. After obtaining an enlarged photograph (200 times) of the cross section of the heater of the present invention in the direction perpendicular to the main surface as shown in Fig. 1, the thickness of the high-strength and high-insulating sheet was randomly determined in the enlarged photograph. Measurements are taken at 100 selected locations and the simple average value is determined. Then, the obtained average value is taken as the thickness of that layer. Regarding the thickness of other layers (first adhesive layer 5, first insulating layer 7, second adhesive layer 9, heat generating layer 11, third adhesive layer 13, second insulating layer 15 and other layers) to be described later. shall also mean a value obtained by measurement using a similar method.
  • the main surface of the first adhesive layer 5 is in close contact with the main surfaces of the high-strength, high-insulating sheet 3 and the first insulating layer 7, respectively.
  • the main surface of the second adhesive layer 9 is in close contact with the main surfaces of the first insulating layer 7 and the heat generating layer 11, respectively.
  • the main surface of the third adhesive layer 13 is in close contact with the main surfaces of the heat generating layer 11 and the second insulating layer 15, respectively.
  • the first adhesive layer 5 is made of the above-described adhesive of the present invention.
  • the second adhesive layer 9 and/or the third adhesive layer 13 may also be made of the adhesive of the invention described above.
  • the thickness of the first adhesive layer 5 is not limited, but is preferably 5 to 50 ⁇ m, more preferably 20 to 30 ⁇ m.
  • the thickness of the second adhesive layer 9 is not limited, but is preferably 5 to 100 ⁇ m, more preferably 20 to 30 ⁇ m.
  • the thickness of the third adhesive layer 13 is not limited, but is preferably 5 to 100 ⁇ m, more preferably 20 to 30 ⁇ m.
  • First insulating layer 7 and the second insulating layer 15 will be explained. These may be of the same embodiment or may be of different embodiments.
  • the main surface of the first insulating layer 7 is in close contact with the main surfaces of each of the first adhesive layer 5 and the second adhesive layer 9.
  • the first insulating layer 7 serves to electrically insulate the heat generating layer 11 and the high-strength, high-insulating sheet 3.
  • the main surface of the second insulating layer 15 is in close contact with the main surface of the third adhesive layer 13.
  • the second insulating layer 15 plays a role of electrically insulating that layer and the heat generating layer 11. Fulfill.
  • first insulating layer 7 and the second insulating layer 15 have thermal conductivity in addition to insulation.
  • the first insulating layer 7 and the second insulating layer 15 are, for example, PET (polyethylene terephthalate), PI (polyimide), PP (polypropylene), PE (polyethylene), PEN (polyethylene naphthalate), TAC (triacetyl cellulose), ceramic It is preferable that it consists of the following. This is because these have high insulation properties. Among these, the first insulating layer 7 and the second insulating layer 15 made of PI (polyimide) are preferable because they have excellent heat resistance and insulation properties.
  • the thickness (h 1 ) of the first insulating layer 7 is not limited, but is preferably 25 to 75 ⁇ m, more preferably 40 to 60 ⁇ m.
  • the thickness of the second insulating layer 15 is not limited, but is preferably 10 to 50 ⁇ m, more preferably 20 to 30 ⁇ m.
  • the shapes and sizes of the main surfaces of the first insulating layer 7 and the second insulating layer 15 are not particularly limited. However, since the first insulating layer 7 and the second insulating layer 15 play a role of electrically insulating the heat generating layer 11 from other layers, the size of the main surface of the first insulating layer 7 and the second insulating layer 15 is is usually the same as the main surface of the heat generating layer 11 or larger than the main surface of the heat generating layer 11 .
  • the ratio ( h 1 /H total ) is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.20 or more.
  • the present inventor has discovered that when the heater of the present invention is placed on a curved surface of an object to be heated such as a pipe, the tensile (elongation) stress load can be further reduced. I found it.
  • sheet heaters have been required to be as thin as possible from the viewpoint of ease of installation on curved surfaces such as piping, specifically ease of wrapping around the outside of piping and ease of heat transfer. was.
  • the inventors have found that simply making the heat generating element thinner increases the tensile (elongation) stress load, and there is a concern that resistance value changes may occur as the heating element elongates. Even if the overall thickness of the sheet heater is made thinner, the thickness (h 1 ) of the first insulating layer is not made thinner, but rather thicker. By setting the ratio (h 1 /H total ) of the thickness of the first insulating layer (h 1 ) to the total thickness of the adhesive layer and the first insulating layer (H total ) to be 0.10 or more, The present inventor has discovered that the tensile (elongation) stress load can be further reduced.
  • the heat generating layer 11 may be a sheet-like layer that generates heat when energized.
  • the heat generating layer 11 may be, for example, a metal foil, a sheet-like metal mesh, a sheet-like metal fiber, or a carbon sheet.
  • the material of the heat generating layer 11 is not particularly limited as long as it generates heat when energized, and is preferably stainless steel, but may be Cu (copper), Al (aluminum), Ni (nickel), nichrome, or carbon. You can.
  • the thickness of the heat generating layer 11 is preferably 10 to 600 ⁇ m, more preferably 20 to 150 ⁇ m, and preferably about 30 ⁇ m from the viewpoint of flexibility and strength.
  • the shape and size of the main surface of the heat generating layer 11 can be adjusted as appropriate depending on the shape and size of the object to be heated on which the sheet of the present invention is installed.
  • the resistance value of the heat generating layer 11 is preferably 10 to 800 ⁇ , more preferably 80 to 200 ⁇ . If this resistance value is too low, there is a possibility that the temperature will become excessive due to excessive output, and conversely, if the resistance value is too high, the temperature may take time to rise due to insufficient output.
  • the resistance of the heat generating layer is a value determined in accordance with JIS K 7194.
  • the heat generating layer 11 mainly consists of metal fibers, and more preferably consists only of metal fibers.
  • “mainly” means 70% by mass or more. That is, it is preferable that 70% by mass or more of the heat generating layer 75 is made of metal fibers.
  • the proportion of metal fibers contained in the heat generating layer 75 is more preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the proportion of metal fibers contained in the heat generating layer 11 shall be specified by the following method.
  • SEM scanning electron microscope
  • the area of the metal fibers (excluding voids) occupying the field of view is calculated using an image processing device.
  • the metal fiber content is calculated by multiplying by the specific gravity to obtain the mass ratio.
  • the metal fiber is preferably a metal fiber whose cross section has a diameter equivalent to an equal area circle of 2 to 100 ⁇ m (preferably 5 to 20 ⁇ m) and a length of 2 to 20 mm.
  • the heat generating layer 11 is formed into a sheet-like structure (metal fiber sheet) in which countless such metallic fibers are intertwined in a complicated manner.
  • the metal fiber sheet may consist only of metal fibers, but in addition to metal fibers, it may also contain other materials (for example, resin fibers that function as a binder) as long as they do not impede heat generation properties.
  • the metal fibers constituting the metal fiber sheet are in contact with each other to the extent that they conduct electricity.
  • the metal fibers are connected to each other at contact points.
  • the metal fibers have a history of being partially melted and solidified by sintering at a high temperature, so that the metal fibers are fused to each other at the contact points.
  • the metal fiber sheet is preferably a SUS fiber sheet because it has high heat resistance and chemical resistance.
  • SUS fiber sheet include a stainless steel fiber sheet (for example, Tomy Firec SS, manufactured by Tomegawa Paper Manufacturing Co., Ltd.).
  • the basis weight of the metal fiber sheet is preferably 25 g/m 2 or more, more preferably 50 g/m 2 or more. Further, it is preferably 1000 g/m 2 or less, more preferably 200 g/m 2 or less. Note that the basis weight is a value determined in accordance with JIS P 8124.
  • the metal fiber sheet can be manufactured by a dry nonwoven fabric manufacturing method or a wet paper forming method.
  • a dispersion medium water, organic solvent, etc.
  • an organic flocculant, etc. are added, and the sheet is formed into a sheet using a square hand-sheeting device (manufactured by Toyo Seiki Co., Ltd., etc.), and a dry sheet with a basis weight of 50 to 1100 g/m 2 is obtained using a ferrotype drying device. Thereafter, a metal fiber sheet is obtained by firing at 400 to 1300°C.
  • the heater 1 of the present invention includes the high-strength and high-insulating sheet 3, the first adhesive layer 5, the first insulating layer 7, the second adhesive layer 9, the heat generating layer 11, (preferably further The three adhesive layers 13 and the second insulating layer 15 are laminated in this order, and the main surfaces of the adjacent layers are in close contact with each other. Further, a heat diffusion layer may be further provided on the main surface of the high-strength, high-insulating sheet 3 on which the first adhesive layer 5 is not attached. When the heat diffusion layer is provided, the heat generated by the heat generating layer can be diffused, and the object to be heated can be heated more uniformly.
  • the method of bonding the heat diffusion layer to the main surface of the high-strength, high-insulating sheet 3 on which the first adhesive layer 5 is not attached is not particularly limited, but bonding may be performed using the adhesive of the present invention described above. preferable.
  • the thermal conductivity of the heat diffusion layer in its in-plane direction is higher than that of the heat-generating layer in its in-plane direction. This is because the thermal diffusion ability is further increased.
  • the thermal conductivity of the thermal diffusion layer can be measured using known measurement methods such as laser flash method thermal diffusivity measurement (e.g., LFA series manufactured by NETZSCH), optical alternating current method thermal diffusivity measurement (e.g. LaserPit series manufactured by Advance Riko), etc. Measured at room temperature.
  • the heat diffusion layer is preferably made of metal such as carbon, aluminum, copper, zinc, lead, gold, or silver, or ceramic such as alumina or aluminum nitride.
  • the heat diffusion layer is preferably made of carbon film. This is because it has excellent flexibility and high thermal conductivity in the extending direction.
  • the thickness of the heat diffusion layer is not particularly limited, but is preferably 5 to 300 ⁇ m, more preferably 15 to 200 ⁇ m, and even more preferably about 100 ⁇ m.
  • the total thickness of the sheet of the present invention is not limited, it is preferably 200 to 800 ⁇ m, more preferably 200 to 500 ⁇ m, and even more preferably 300 to 450 ⁇ m.
  • Example 1 A sheet-like heater of the embodiment shown in FIG. 1 was prepared. Details of each layer are as follows. ⁇ High strength and high insulation sheet: PTFE cloth (manufactured by Chukoh Kasei Kogyo Co., Ltd., FGF-500-8), thickness 170 ⁇ m ⁇ First adhesive layer: layer made of fluorine adhesive, thickness 25 ⁇ m ⁇ First insulating layer: polyimide film, thickness 50 ⁇ m ⁇ Second adhesive layer: Same as the first adhesive layer (thickness 25 ⁇ m) ⁇ Heating layer: Stainless steel paper (Tomy Firec SS, manufactured by Tomoekawa Paper Manufacturing Co., Ltd.), thickness 30 ⁇ m ⁇ Third adhesive layer: Same as first adhesive layer and second adhesive layer (thickness 25 ⁇ m) ⁇ Second insulating layer: Same as first insulating layer (thickness 25 ⁇ m)
  • the thickness of each layer is a value obtained by measurement using the method described above.
  • the fluorine-based adhesive used to form the first adhesive layer, second adhesive layer, and third adhesive layer has a solubility in the range of 5 to 30% by mass when subjected to the above-mentioned solvent solubility test. This is a fluorine-based adhesive.
  • a high power general purpose stirrer BLH1200 manufactured by Shinto Kagaku Co., Ltd. was used as a medium stirrer.
  • the fluorine content of this fluorine-based adhesive was measured by the method described above, it was within the range of 57 to 60% by mass. Furthermore, when the unsaturated bond content of this fluorine-based adhesive was measured using the method described above, it was within the range of 0.1 to 10%. Furthermore, the storage modulus (E 1 ) of this fluorine-based adhesive at 25° C. was measured using the method described above, and was found to be 5.58 MPa. Furthermore, the storage modulus (E 2 ) of this fluorine-based adhesive at 70° C. was measured using the method described above, and was found to be 3 MPa.
  • the strain (gauge value) of the sheet-like heater obtained in Example 1 was measured.
  • the method for measuring strain (gauge value) is as follows. After fixing the strain gauge of the strain measuring device (FLAB-1-11-3LJCT manufactured by Tokyo Sokki Institute) on the upper side of the heating element layer in the same direction as the winding direction, the adhesive layer 13 and A third insulating layer 15 is laminated. The strain is defined as zero immediately after lamination, and the strain gauge value is read when the layer is wound around a ⁇ 27 mm cylinder.
  • Table 1 also shows the elongation (%) value calculated as a value of 1/10,000 of the gauge value.
  • Example 2 The same experiment as in Example 1 was conducted except that the thickness of the first insulating layer was 25 ⁇ m. The results are shown in Table 1.
  • Example 3 The same experiment as in Example 1 was conducted except that PTFE cloth (manufactured by Chukoh Kasei Kogyo Co., Ltd., FGF-500-10) with a thickness of 250 ⁇ m was used as the high strength and high insulating sheet. The results are shown in Table 1.
  • Example 4 The same experiment as in Example 1 was conducted except that the thickness of the first adhesive layer was 50 ⁇ m. The results are shown in Table 1.
  • Example 5 A layer made of a fluorine-based adhesive (25 ⁇ m thick) and a polyimide film (50 ⁇ m thick) were additionally formed between the first insulating layer and the second adhesive layer in Example 1. That is, a high-strength, high-insulating sheet, a first adhesive layer, a first insulating layer, a layer made of fluorine adhesive (thickness 25 ⁇ m), a polyimide film (thickness 50 ⁇ m), a second adhesive layer, a heat generating layer, and a third layer. The adhesive layer and the second insulating layer were laminated in this order. The same experiment as in Example 1 was conducted except for the above. The results are shown in Table 1.
  • Example 6 As the high-strength, high-insulating sheet, PTFE cloth (manufactured by Chukoh Kasei Kogyo Co., Ltd., FGF-500-10) with a thickness of 250 ⁇ m was used, and the thickness of the first insulating layer was 25 ⁇ m. The same experiment was conducted. The results are shown in Table 1.
  • Example 7 As a high-strength, high-insulating sheet, PTFE cloth (FGF-500-10 manufactured by Chukoh Kasei Kogyo Co., Ltd.) with a thickness of 250 ⁇ m was used, the thickness of the first adhesive layer was 50 ⁇ m, and the thickness of the first insulating layer was 25 ⁇ m.
  • the same experiment as in Example 1 was conducted except for the following. The results are shown in Table 1.
  • the adhesive used here was the same as that used to form the first adhesive layer, and the thickness of the adhesive layer X made of the adhesive used to attach this aluminum layer was 25 ⁇ m. .
  • the same experiment as in Example 6 was conducted except for this. The results are shown in Table 1.
  • Example 9 As the high-strength, high-insulating sheet, PTFE cloth (manufactured by Chukoh Kasei Kogyo Co., Ltd., FGF-500-2) with a thickness of 50 ⁇ m was used, and the thickness of the first insulating layer was 25 ⁇ m. The same experiment was conducted. The results are shown in Table 1.
  • Example 10 The same experiment as in Example 1 was conducted except that PTFE cloth (manufactured by Chukoh Kasei Kogyo Co., Ltd., FGF-500-6) with a thickness of 125 ⁇ m was used as the high strength and high insulating sheet.
  • Example 11 The same experiment as in Example 1 was conducted except that the thickness of the first adhesive layer was 20 ⁇ m. The results are shown in Table 1.
  • Example 12 The same experiment as in Example 1 was conducted except that the thickness of the first insulating layer was 75 ⁇ m. The results are shown in Table 1.
  • the heater of the present invention using the adhesive of the present invention has a lower elongation % and is preferable.
  • Example 13 As mentioned above, in Example 1, in order to form the first adhesive layer, the second adhesive layer, and the third adhesive layer, a fluorine-based material whose solubility obtained when subjected to a solvent solubility test was within the range of 5 to 30% by mass was used. Glue was used. On the other hand, in Example 13, as in Example 1, the solubility obtained by subjecting to the solvent solubility test was within the range of 5 to 30% by mass, and the storage modulus (E 1 ) at 25°C was 70%.
  • the first adhesive layer, the second adhesive layer, and the third adhesive layer are formed using a fluorine-based adhesive having a storage modulus (E 2 ) ratio (percentage: E 2 /E 1 ⁇ 100) of 50% at °C. was formed.
  • the thickness of these layers was 25 ⁇ m, the same as in Example 1.
  • a sheet-like heater was created by using the same high-strength, high-insulating sheet, first insulating layer, heating layer, and second insulating layer as in Example 1. Thereafter, a test was conducted in which such a sheet-shaped heater was wound around a stainless steel pipe having an outer diameter of 42.7 mm and an inner diameter of 35.7 mm. Specifically, the details are as follows.
  • the stainless steel piping and sheet heater were placed in an oven whose interior was adjusted to 110° C., and heated for 30 minutes.
  • the sheet heater was wrapped around the stainless steel piping and held in that state for 10 minutes.
  • the stainless steel pipe around which the sheet heater was wrapped was taken out of the oven in that state and left to cool indoors until it reached room temperature.
  • the sheet heater was removed from the stainless steel piping, and the inner diameter of the sheet heater, which had a cylindrical shape or a part thereof, was measured.
  • the inner diameter was compared with the outer diameter (42.7 mm) of the stainless steel pipe.
  • Example 14 In Example 13, the first adhesive layer, the second adhesive layer, and the third adhesive layer were subjected to a solvent solubility test in the same manner as in Example 1, and the obtained solubility was within the range of 5 to 30% by mass, and 25% by mass. It was formed using a fluorine-based adhesive with a ratio of storage elastic modulus (E 2 ) at 70°C to storage elastic modulus (E 1 ) at 70°C (percentage: E 2 /E 1 ⁇ 100) of 50%.
  • E 2 storage elastic modulus
  • E 1 storage elastic modulus
  • Example 14 as in Example 1, the solubility obtained by subjecting to the solvent solubility test was within the range of 5 to 30% by mass, and the storage modulus at 70°C relative to the storage modulus (E 1 ) at 25°C It was formed using a fluorine-based adhesive having a ratio (E 2 ) of 70% (percentage: E 2 /E 1 ⁇ 100). Other than that, the same operations as in Example 13 were performed to create a sheet-like heater, and the same tests were conducted. The results are shown in Table 2.
  • Example 13 the first adhesive layer, the second adhesive layer, and the third adhesive layer were subjected to a solvent solubility test in the same manner as in Example 1, and the obtained solubility was within the range of 5 to 30% by mass, and 25% by mass. It was formed using a fluorine-based adhesive with a ratio of storage elastic modulus (E 2 ) at 70°C to storage elastic modulus (E 1 ) at 70°C (percentage: E 2 /E 1 ⁇ 100) of 50%.
  • Example 1 the first adhesive layer, the second adhesive layer, and the third adhesive layer have a ratio (percentage: E 2 ) of the storage modulus at 70°C (E 2 ) to the storage modulus (E 1 ) at 25°C /E 1 ⁇ 100) of 5%.
  • E 2 percentage: 70°C
  • E 1 storage modulus
  • Table 2 percentage: 25°C /E 1 ⁇ 100
  • Example 13 the first adhesive layer, the second adhesive layer, and the third adhesive layer were subjected to a solvent solubility test in the same manner as in Example 1, and the obtained solubility was within the range of 5 to 30% by mass, and 25% by mass. It was formed using a fluorine-based adhesive with a ratio of storage elastic modulus (E 2 ) at 70°C to storage elastic modulus (E 1 ) at 70°C (percentage: E 2 /E 1 ⁇ 100) of 50%. In Example 2, the first adhesive layer, the second adhesive layer, and the third adhesive layer have a ratio (percentage : E 2 ) of the storage modulus (E 2 ) at 70°C to the storage modulus (E 1 ) at 25°C. /E 1 ⁇ 100) of 100%. Other than that, the same operations as in Example 13 were performed to create a sheet-like heater, and the same tests were conducted. The results are shown in Table 2.
  • Example 13 and Example 14 were able to have a good curl.
  • the sheet-like heaters of Comparative Examples 1 and 2 were unable to form a good curl.
  • Heater of the present invention 3 High-strength, high-insulating sheet 5 First adhesive layer 7 First insulating layer 9 Second adhesive layer 11 Heat generating layer 13 Third adhesive layer 15 Second insulating layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Resistance Heating (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un adhésif à base de fluor à utiliser dans un élément chauffant en forme de feuille qui est hautement isolant et qui est apte à réduire la charge de contrainte par traction (étirement) lorsqu'il est disposé sur une surface incurvée telle qu'un tuyau. Le problème est résolu par un adhésif à base de fluor qui, lorsqu'il est soumis à un test de solubilité dans un solvant, a une solubilité comprise entre 5 et 30 % en masse, et qui est utilisé pour faire adhérer les couches d'un élément chauffant en forme de feuille présentant une structure stratifiée. Dans le test de solubilité dans un solvant, du tétrahydrofurane (THF) est introduit dans une bouteille en plastique de 2l en une quantité de 1 000 g et ajusté à 23 °C. Le tétrahydrofurane (THF) est agité à 600 tr/min à l'aide d'un agitateur pour viscosité moyenne qui utilise, en tant que pale d'agitation, une pale de dispersion présentant un diamètre de 40 mm. Pendant l'agitation, 1 à 50 g d'un échantillon particulaire présentant un diamètre compris entre 0,5 et 2,0 cm est introduit, et après 24 heures, il est confirmé si toute la quantité de ce dernier s'est dissoute ou non. Si toute la quantité s'est dissoute, le processus d'ajout de 1 à 50 g supplémentaires d'échantillon et la confirmation après 24 heures que toute la quantité de ce dernier est répété, et ainsi la quantité soluble maximale (solubilité) est déterminée.
PCT/JP2023/005506 2022-03-30 2023-02-16 Élément chauffant en forme de feuille et adhésif à base de fluor utilisé dans ce dernier WO2023188956A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10188992A (ja) * 1996-12-24 1998-07-21 Sony Corp 非水電解液電池
JP2001525104A (ja) * 1996-08-29 2001-12-04 グレヴィック，アーサー 発熱体とその製造方法
JP2005116490A (ja) * 2003-10-03 2005-04-28 Meiji Shigeno 柔軟面状発熱体
JP2007224208A (ja) * 2006-02-24 2007-09-06 Alpha Oikos:Kk フッ素ゴムシート及びフッ素ゴムシートを用いた面状ヒーター及びその製造方法
JP2015122212A (ja) * 2013-12-24 2015-07-02 日本バルカー工業株式会社 面状ヒーター
JP2016120683A (ja) * 2014-12-25 2016-07-07 三井化学株式会社 積層構造物、光硬化性組成物および積層構造物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001525104A (ja) * 1996-08-29 2001-12-04 グレヴィック，アーサー 発熱体とその製造方法
JPH10188992A (ja) * 1996-12-24 1998-07-21 Sony Corp 非水電解液電池
JP2005116490A (ja) * 2003-10-03 2005-04-28 Meiji Shigeno 柔軟面状発熱体
JP2007224208A (ja) * 2006-02-24 2007-09-06 Alpha Oikos:Kk フッ素ゴムシート及びフッ素ゴムシートを用いた面状ヒーター及びその製造方法
JP2015122212A (ja) * 2013-12-24 2015-07-02 日本バルカー工業株式会社 面状ヒーター
JP2016120683A (ja) * 2014-12-25 2016-07-07 三井化学株式会社 積層構造物、光硬化性組成物および積層構造物の製造方法

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