WO2021157532A1 - Heat-generating film and method for manufacturing heat-generating film - Google Patents
Heat-generating film and method for manufacturing heat-generating film Download PDFInfo
- Publication number
- WO2021157532A1 WO2021157532A1 PCT/JP2021/003560 JP2021003560W WO2021157532A1 WO 2021157532 A1 WO2021157532 A1 WO 2021157532A1 JP 2021003560 W JP2021003560 W JP 2021003560W WO 2021157532 A1 WO2021157532 A1 WO 2021157532A1
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- WIPO (PCT)
- Prior art keywords
- heat
- conductive portion
- generating film
- transparent
- conductive
- Prior art date
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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
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- 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
-
- 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
Definitions
- the present invention relates to a heat-generating film and a method for producing a heat-generating film.
- Vehicles such as automobiles may be provided with a mechanism to prevent adhesion of fogging, frost, water droplets, etc. on windows and mirrors in order to maintain good visibility of the driver while driving.
- the rear window of an automobile is provided with a defogger consisting of a heating wire printed on the glass of the rear window. By heating the glass with a defogger heating wire, fogging and frost on the rear window can be removed (for example, Patent Document 1).
- a heater for heating the side mirror to prevent water droplets from adhering is provided (for example, Patent Document 2).
- the heating wire is visually recognized in the defogger, and so-called "bone visibility" occurs. For this reason, the view of the driver of the vehicle is obstructed, and the design of the vehicle is also deteriorated. Since the heater provided on the side mirror is provided on the back surface of the mirror, it does not affect the view of the driver of the vehicle or the design of the vehicle, but the heating efficiency of the mirror is lowered. It is not desirable to provide a heater in front of the side mirrors in order to improve the heating efficiency because it impairs the view of the driver of the vehicle and deteriorates the design of the vehicle.
- the present invention solves the above problems, and provides a heat-generating film capable of efficiently heating vehicle windows, mirrors, etc. while maintaining the visibility of the vehicle driver and the design of the vehicle.
- the heat-generating film has a plurality of first grooves extending in the first direction on the surface and a plurality of second grooves extending in the second direction intersecting the first direction. It is provided with a transparent film having a transparent film and conductive portions existing in the first and second grooves, the line width of the conductive portion is 0.2 to 10 ⁇ m, and the height of the conductive portion is 0.5 to 10 ⁇ m. The distance between the conductive portions existing in the two adjacent first grooves is 20 to 1000 ⁇ m, and the conductive portion existing in the first groove and the conductive portion existing in the second groove.
- a heat-generating film in which the number of intersections with and is 20 to 2500 / cm 2 , and the area ratio of the conductive portion is 0.1 to 10%.
- the light transmittance of the heat-generating film at a wavelength of 550 nm may be 60 to 98%.
- the surface resistance value of the heat-generating film is 0.003 to 70 ⁇ / sq. It may be.
- the distance between the conductive portions existing in the two adjacent second grooves in the first direction may be 1000 to 15000 ⁇ m.
- the second direction may be orthogonal to the first direction.
- a plurality of first double-track portions composed of conductive portions existing in a plurality of first grooves are provided, and two adjacent first double-track portions are arranged at a first interval of 20 to 1000 ⁇ m to form a first double-track portion.
- the plurality of conductive portions may be arranged at a fourth interval smaller than the first interval.
- the fourth interval may be 0.2 to 20 ⁇ m.
- a plurality of second double-track portions composed of conductive portions existing in the plurality of second grooves are provided, and two adjacent second double-track portions are arranged at a second interval in the first direction to form a second double-track portion.
- the plurality of conductive portions may be arranged at a fifth interval smaller than the second interval in the first direction.
- the fifth interval may be 0.5 to 20 ⁇ m.
- the transparent film having the first groove and the second groove is prepared on the surface, and the first groove and the second groove are formed.
- a method for producing a heat-generating film which comprises filling the film with a conductive material to form the conductive portion.
- Preparing the transparent film may include forming a first groove and a second groove on the transparent film by imprinting using a mold having a concavo-convex pattern corresponding to the conductive portion.
- the transparent film has a transparent support base material and a transparent resin layer formed on the transparent support base material, and preparing the transparent film provides the mold having an uneven pattern corresponding to the conductive portion.
- To prepare to apply a photocurable resin to the surface of the mold on which the uneven pattern is formed to form a coating layer, and to arrange the transparent support base material on the coating layer. And, the coating layer may be cured by irradiating the transparent support base material side with ultraviolet light to form the transparent resin layer, and the mold may be peeled off from the transparent resin layer.
- the conductive portion may be formed by electroless plating.
- the heat-generating film of the present invention can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generation when energized. Therefore, it can be used as a heat-generating film that can efficiently heat the windows, mirrors, etc. of the vehicle while maintaining the visibility of the driver of the vehicle and the design of the vehicle. In addition, the heat-generating film of the present invention is not easily affected by disconnection of the conductive portion, and has high durability and reliability.
- FIG. 1 (a) is a diagram conceptually showing the cross-sectional structure of the heat-generating film of the embodiment
- FIG. 1 (b) is a diagram showing an enlarged cross-sectional structure in the vicinity of the conductive portion shown in FIG. 1 (a).
- FIG. 2 is a heat-generating film of the embodiment, which is a diagram conceptually showing a plane on which a lattice pattern (pattern A) is formed.
- FIG. 3A is a diagram showing another embodiment in which the conductive portion protrudes from the surface of the heat generating film
- FIG. 3B is a diagram showing another embodiment in which the conductive portion is partially filled in the recess. Is.
- FIG. 4 is a flowchart illustrating a method for manufacturing a heat-generating film according to an embodiment.
- 5 (a) to 5 (c) are diagrams conceptually showing a process of manufacturing a transparent film including a transparent resin layer in which lattice-shaped recesses are formed on the surface in a method for manufacturing a heat-generating film.
- 6 (a) to 6 (c) are diagrams conceptually showing steps required for electroless plating in a method for producing a heat-generating film.
- FIG. 7A is a diagram conceptually showing the plane of the heat-generating film of another embodiment in which the lattice pattern (pattern D1) is formed
- FIG. 7B is a diagram in which the lattice pattern (pattern D2) is formed.
- FIG. 8 is a diagram conceptually showing the plane of the heat generating film of another embodiment in which the lattice pattern (pattern E) is formed.
- FIG. 9 is a diagram conceptually showing the plane of a conventional heat-generating film on which a line / space (L / S) pattern F is formed.
- the heat-generating film 10 of the present embodiment is formed on a transparent film 11 composed of a transparent support base material 33 and a transparent resin layer 12 formed on the transparent support base material 33, and on the transparent film 11.
- the conductive portion 13 is provided.
- the transparent resin layer 12 has a recess (groove) 11c having a rectangular cross section.
- the recess 11c has a first groove 11A extending in the first direction and a second groove 11B extending in the second direction intersecting the first direction on the surface 11s of the transparent film 11.
- the recess (groove) 11c including the first groove 11A and the second groove 11B is a lattice groove that forms a grid-like pattern (pattern A) in a plan view of the heat generating film 10.
- pattern A the first direction and the second direction are orthogonal to each other.
- the conductive portion 13 is formed by filling the recess 11c of the transparent film 11 with a conductive material. That is, the conductive portion 13 exists in the recess 11c.
- the conductive portion 13 includes a first conductive portion 13A filled in the first groove 11A and a second conductive portion 13B filled in the second groove 11B. As shown in FIG.
- the first conductive portion 13A and the second conductive portion 13B are in a grid pattern, and a grid pattern (pattern A) is formed on the surface 11a of the transparent film 11.
- a grid pattern pattern A
- these are collectively referred to as a recess (groove, lattice groove) 11c.
- the conductive portion 13A and the second conductive portion 13B are collectively referred to as the conductive portion 13.
- the transparent film 11 has a transparent support base material 33 and a transparent resin layer 12 laminated on the transparent support base material 33.
- resins such as photocurable, thermosetting, moisture-curable, and chemically curable (two-component mixture) can be used.
- resins such as photocurable, thermosetting, moisture-curable, and chemically curable (two-component mixture)
- resins such as photocurable, thermosetting, moisture-curable, and chemically curable (two-component mixture)
- epoxy-based acrylic-based, methacrylic-based, vinyl ether-based, oxetane-based, urethane-based, melamine-based, urea-based, polyester-based, polyolefin-based, phenol-based, crosslinked liquid crystal-based, fluorine-based, and silicone-based.
- the thickness of the transparent resin layer 12 may be in the range of 0.5 to 500 ⁇ m, 1 to 400 ⁇ m, 5 to 200 ⁇ m, or 2 to 20 ⁇ m. If the thickness is less than the lower limit, the depth of the recess 11c formed in the transparent resin layer 12 tends to be insufficient, and if the thickness exceeds the upper limit, there is a concern that the influence of the volume change of the resin that occurs during curing becomes large.
- the transparent support base material 33 a known film base material that transmits visible light can be used.
- a base material made of a transparent inorganic material such as glass; polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.), (meth) acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, etc.
- a substrate made of a resin such as a styrene resin (ABS resin or the like), a cellulose resin (triacetyl cellulose or the like), a polyimide resin (polyimide resin, a polyimide amide resin or the like), a cycloolefin polymer or the like can be used.
- the transparent support base material 33 may be a resin film.
- the thickness of the transparent support base material 33 is preferably 1 to 500 ⁇ m, 10 to 300 ⁇ m, or 20 to 150 ⁇ m from the viewpoint of optical characteristics. If it is thinner than 1 ⁇ m, the function as a supporting base material may be impaired, and if it is thicker than 500 ⁇ m, the light transmission may not be sufficient.
- the conductive portion 13 generates heat when energized. Therefore, the conductive portion 13 is a heat generating portion of the heat generating film 10. As shown in FIG. 1B, the conductive portion 13 is formed so as to fill the recess (groove) 11c of the transparent film 11, and does not protrude outside the film of the recess 11c in the in-plane direction. In the present embodiment, there is no step between the upper surface 13s of the conductive portion 13 (the portion exposed from the groove) and the surface 11s of the transparent film 11, and both are located in the same plane. That is, the depth D of the recess 11c and the height H of the conductive portion 13 are substantially the same.
- the surface 11s of the transparent film 11 means a surface portion of the transparent film 11 excluding the recess 11c.
- the line width W of the conductive portion 13 is 0.2 to 10 ⁇ m, preferably 0.5 to 10 ⁇ m, 0.7 to 8 ⁇ m, 0.9 to 6 ⁇ m, or 1 to 5 ⁇ m. If the line width W of the conductive portion 13 exceeds the upper limit of the above range, the conductive portion 13 becomes visible, bones are visible, and the transparency (transmittance) of the heat-generating film 10 may decrease. Further, if the line width W of the conductive portion 13 is less than the lower limit of the above range, the conductivity may be insufficient and the amount of heat generated may be insufficient. In addition, the risk of disconnection of the conductive portion 13 increases, and the durability and reliability of the heat generating film 10 decrease.
- the line width W of the conductive portion 13 is the maximum value of the width of the conductive portion 13 in the cross section perpendicular to the direction in which the conductive portion 13 extends.
- the first conductive portion 13A and the second conductive portion 13B have the same line width W.
- the present embodiment is not limited to this, and the first conductive portion 13A and the second conductive portion 13B may have different line widths W.
- the height H of the conductive portion 13 is 0.5 to 10 ⁇ m, preferably 0.7 to 7 ⁇ m, 1 to 5 ⁇ m, or 2 to 4 ⁇ m. If the height H of the conductive portion 13 exceeds the upper limit of the above range, it becomes difficult to form a lattice pattern. Further, if the height H of the conductive portion 13 is less than the lower limit of the above range, the conductivity may be insufficient and the amount of heat generated may be insufficient. The durability and reliability of the heat-generating film 10 are reduced.
- the height H of the conductive portion 13 is the maximum value of the distance (thickness of the conductive portion 13) from the bottom of the concave portion 11c to the surface 13s of the conductive portion 13.
- the first conductive portion 13A and the second conductive portion 13B have the same height H. However, the present embodiment is not limited to this, and the first conductive portion 13A and the second conductive portion 13B may have different heights H, respectively.
- the height H of the conductive portion 13 is preferably 0.1 times or more, 0.1 to 5 times, or 0.5 to 2 times the line width W of the conductive portion 13.
- the aspect ratio of the cross-sectional shape on the plane perpendicular to the extending direction of the conductive portion 13 may be preferably in the range of 1:10 to 5: 1 or 1: 2 to 2: 1.
- the conductive portion 13 of the present embodiment is one or more times the line width W
- the conductive portion 13 can have sufficient conductivity and heat generation.
- the heat-generating film 10 can achieve both a good appearance without bone visibility and high conductivity.
- the height H of the conductive portion 13 is larger than 5 times the line width W, the visibility may be lowered when the heat generating film 10 is viewed from an angle.
- the depth D of the recess 11c and the height H of the conductive portion 13 do not have to be equal.
- the height H of the conductive portion 13 may be higher than the depth D of the recess 11c. That is, the raised portion 13x of the conductive portion 13 (the portion higher than the surface 11s of the transparent film 11) may be present. Even so, the raised portion 13x does not protrude to the outside of the recess 11c in the inward direction of the substrate surface. By doing so, the cross-sectional area of the conductive portion 13 can be increased, and as a result, the resistance value of the conductive portion 13 can be lowered without increasing the area ratio (coverage ratio) of the conductive portion 13 in the lattice pattern.
- the height of the raised portion 13x (height from the surface 11s) is preferably 0.5 ⁇ m or less. If it exceeds 0.5 ⁇ m, the wear resistance of the conductive portion decreases.
- the ratio (H / D) of the height H of the conductive portion 13 to the depth D of the recess 11c is 1.0 ⁇ H / D ⁇ 1.2, 1.0 ⁇ H / D ⁇ 1 from the viewpoint of wear resistance. It is preferably .15 or 1.0 ⁇ H / D ⁇ 1.10 (however, the height of the raised portion 13x is 0.5 ⁇ m or less).
- the conductive portion 13 may be lower than the depth of the recess 11c, and the conductive portion 13 may be partially filled inside the recess 11c.
- the ratio (H / D) of the height H of the conductive portion 13 to the depth D of the recess 11c is 0.1 ⁇ H / D, 0.3 ⁇ H / D, or 0 from the viewpoint of ensuring conductivity. It is preferable that .5 ⁇ H / D.
- a plurality of conductive portions 13 (first conductive portion 13A and second conductive portion 13B) having the same line width W and the same height H are regularly arranged in a grid pattern. They intersect to form a grid pattern (lattice pattern A) on the surface 11s of the transparent film 11. Since the first conductive portion 13A and the second conductive portion 13B are orthogonal to each other, the conductive portion 13 is evenly dispersed in a plan view, whereby the appearance of bones is suppressed and the transparency is improved. Further, the pattern A has a plurality of intersections R where the first conductive portion 13A and the second conductive portion 13B intersect (orthogonally). Although the details will be described later, since the pattern A has the intersection R, the heat-generating film 10 of the present embodiment is not easily affected by the disconnection of the conductive portion 13, and has high durability and reliability.
- the distance between the conductive portions filled in the two adjacent first conductive portions 11A is 20 to 1000 ⁇ m, preferably 50 to 800 ⁇ m. It is 80 to 600 ⁇ m or 90 to 500 ⁇ m. If the first interval P1 is less than the lower limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease. Further, if the first interval P1 exceeds the upper limit of the above range, the amount of heat generated by the heat generating film 10 may be insufficient. Further, since the number of intersections R is reduced, the heat generating film 10 is easily affected by the disconnection of the conductive portion 13, and the durability and reliability may be lowered.
- the first interval P1 is a distance (interval) between two adjacent first conductive portions 13A in a direction perpendicular to the first direction.
- the first interval P1 is a distance (interval) in the second direction.
- the first interval P1 is the distance between the opposing edges (ends) of the two adjacent first conductive portions 13A in the direction perpendicular to the first direction.
- the distance between the conductive portions filled in the two adjacent second conductive portions 11B in the first direction, that is, the second distance P2 between the two adjacent second conductive portions 13B in the first direction is not particularly limited. .. From the viewpoint of achieving both the transparency of the heat-generating film 10 and the amount of heat generated, it may be, for example, 20 to 20000 ⁇ m, 50 to 15000 ⁇ m, 80 to 6000 ⁇ m, or 90 to 3000 ⁇ m.
- the second interval P2 is in the above range, high transparency (transmittance) can be realized.
- the second interval P2 is larger (wider) than the first interval P1, but the present embodiment is not limited to this.
- the first interval P1 and the second interval P2 may be the same or different. However, from the viewpoint of suppressing the appearance of bones in the conductive portion 13 and increasing the transparency (transmittance), it is preferable that the second interval P2 is larger (wider) than the first interval P1.
- the second interval P2 is the distance between the opposing edges (ends) of the two adjacent second conductive portions 13B in the first direction.
- the first interval P1 and the second interval P2 may affect the appearance of the bone of the conductive portion 13 together with the line width W of the conductive portion 13. Although it depends on the size of the line width W of the conductive portion 13, when the first interval P1 and the second interval P2 become smaller (narrower), the bone appearance of the conductive portion 13 may be further suppressed. It is presumed that this is because the human eye cannot recognize the sizes of the first interval P1 and the second interval P2, and the lattice pattern of the conductive portion 13 becomes less noticeable.
- the first interval P1 is less than 300 ⁇ m and the second interval P2 is 5000 ⁇ m or less because the appearance of bone is further suppressed.
- the second interval P2 is preferably 1000 or more, for example. Therefore, in order to suppress the appearance of bone and obtain high transparency, for example, when the line width W of the conductive portion 13 is 2 ⁇ m or less, the first interval P1 is less than 300 ⁇ m and the second interval P2 is 1000. It is preferably about 5000 ⁇ m or less.
- the number of intersections R in the grid-like conductive portion 13, that is, the number of intersections R between the first conductive portion 13A existing in the first groove 11A and the second conductive portion 13B existing in the second groove 11B is determined. It is 20 to 2500 pieces / cm 2 , preferably 30 to 2000 pieces / cm 2 or 50 to 1500 pieces / cm 2 .
- the periphery of the disconnected portion cannot be energized and heat cannot be generated, and a part of the surface 11s of the heat generating film 10 cannot function as the heat generating film. ..
- the area that cannot contribute to heat generation due to the disconnection of the conductive portion 13 at one location is defined as the “disconnection-affected area”.
- the larger the number of intersections R the smaller the area affected by disconnection. That is, the larger the number of intersections R, the less susceptible the heat-generating film 10 is to the disconnection of the conductive portion 13, and the higher the durability and reliability of the heat-generating film 10. If the number of intersections R in the lattice pattern is less than the lower limit of the above range, the heat-generating film 10 cannot obtain sufficient durability and reliability. On the contrary, if the number of intersections R in the lattice pattern exceeds the upper limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease.
- the area ratio of the conductive portion 13 is 0.1 to 10%, preferably 0.2 to 3% or 0.3 to 1%. If the area ratio of the conductive portion 13 is less than the lower limit of the above range, the calorific value may be insufficient. If the area ratio of the conductive portion 13 exceeds the upper limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease.
- the area ratio of the conductive portion 13 is a region in which the grid-like conductive portion 13 on the surface of the heat-generating film 10 is formed (a region in which the grid-like pattern A is formed) in the plan view of the heat-generating film 10. It is the coverage of the conductive portion 13 in the above.
- Examples of the material of the conductive portion 13 include metals such as nickel, copper, zinc, chromium, palladium, silver, tin, lead, gold and aluminum, and alloys and compounds of these metals. From the viewpoint of conductivity, metals such as nickel, copper, silver and gold, and alloys and alloys of these metals are preferable, and from the viewpoint of flexibility, metals or alloys such as silver, copper and nickel are preferable.
- the light transmittance of the heat-generating film 10 of the present embodiment at a wavelength of 550 nm is preferably 60 to 98%, 80 to 95%, or 85 to 92%. When the transmittance is within the above range, the heat-generating film 10 has sufficient transparency.
- the surface resistance value of the heat generating film 10 of the present embodiment is preferably 0.003 to 70 ⁇ / sq. , 0.05 to 30 ⁇ / sq. Or 0.1 to 20 ⁇ / sq. May be. When the surface resistance value is in this range, the heat generating film 10 can obtain a sufficient amount of heat generated when energized.
- the heating rate of the heat generating film 10 of the present embodiment is preferably 0.02 to 0.5 ° C./sec., 0.03 to 0.4 ° C./sec., Or 0.04 to 0.3 ° C./sec. It may be sec. When the heating rate is within this range, the heat-generating film can exhibit sufficient heat-generating characteristics when energized.
- the rate of temperature rise can be measured, for example, by the measurement method and measurement conditions described in Examples described later.
- the heat-generating film 10 may include a lead-out wiring connected to the end of the conductive portion 13 in order to energize the conductive portion 13 to generate heat.
- the lead-out wiring may be at the same height as the upper surface 13s of the conductive portion 13, and in particular, there is no step between the upper surface 13s of the conductive portion 13 and the surface 11s of the transparent film 11a, and both are located in the same plane. You can.
- the material of the lead-out wiring the same material as those exemplified as the material of the conductive portion 13 can be used.
- the heat-generating film 10 of the present embodiment can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generated when energized. Further, the heat-generating film of the present embodiment is not easily affected by the disconnection of the conductive portion, and has high durability and reliability. Therefore, the heat-generating film 10 of the present embodiment can be used as a heat-generating film that can efficiently heat the windows, mirrors, and the like of the vehicle without deteriorating the visibility of the driver of the vehicle and the design of the vehicle.
- the method for manufacturing the heat-generating film 10 is to prepare a transparent film 11 having lattice grooves 11c (first groove 11A and second groove 11B) formed on the surface 11s (FIG. 4). Step S1) and filling the lattice groove 11c with a conductive material to form the conductive portion 13 (first conductive portion 13A and second conductive portion 13B) (step S2 in FIG. 4).
- the heat-generating film 10 is manufactured, for example, by using a mold having a concavo-convex pattern corresponding to the conductive portion 13, forming a concavo-convex transparent film 11 by imprinting, and then filling the recesses with a conductive member by electroless plating. You may. Hereinafter, specific examples of the method for producing the heat-generating film 10 will be described with reference to FIGS. 5 and 6.
- a mold 20 having a concavo-convex pattern in which rectangular convex portions 20a having a rectangular cross-sectional shape are formed at predetermined intervals is prepared on the surface.
- the uneven pattern of the mold is a lattice pattern in which a plurality of straight lines intersect at predetermined intervals in a plan view (see pattern A in FIG. 2).
- the height and width of the convex portion 20a and the distance between the convex portions 20a are set to be the same as the design dimensions of the conductive portion 13 described above.
- the mold 20 can be produced, for example, by using a photolithography method in which a photoresist applied on a silicon substrate is photosensitiveed and etched through a mask having a predetermined pattern. It is preferable to apply a mold release agent to the surface of the mold 20 for the next step.
- a photocurable resin such as an ultraviolet curable resin is applied to the surface of the mold 20 on which the convex portion 20a is formed to form the coating layer 22.
- a transparent support base material 33 made of a synthetic resin such as a PET film is arranged on the coating layer 22 to form a laminate as shown in FIG. 5 (b).
- the laminated body is irradiated with ultraviolet light from the transparent support base material 33 side.
- the photocurable resin constituting the coating layer 22 is cured to form the transparent resin layer 12.
- the mold 20 is peeled off from the transparent resin layer 12 of the laminated body, and a grid-like concave portion (lattice groove) 11c corresponding to the pattern of the convex portion 20a of the mold is formed on the surface.
- a transparent film 11 including the transparent resin layer 12 is obtained.
- the conductive portion 13 was formed in the recess 11c of the transparent resin layer 12 of the transparent film 11 obtained as described above by electroless plating as follows.
- silane coupling treatment When performing electroless plating, it is preferable to perform a silane coupling treatment on the portion to be plated in order to ensure strong adhesion of the plating film.
- the silane coupling agent used for such treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, and 3-(. Aminosilane compounds such as N-phenyl) aminopropyltrimethoxysilane and other silane compounds having a reactive functional group can be used.
- the base layer 28 is formed on the surface of the transparent resin layer 12 including the recess 11c.
- the transparent film 11 may be heated after applying the solution of the base layer forming material. Further, before applying the solution of the base layer forming material, the surface of the transparent resin layer 12 may be irradiated with UV light to modify the surface of the transparent resin layer 12.
- a treatment is performed so that the base layer 28 exists only on the inner surface of the recess 11c.
- This treatment includes, for example, irradiating only the base layer 28 on the surface of the transparent resin layer 12 excluding the opening of the recess 11c with UV light. If necessary, a mask or the like that blocks light may be used. As a result, as shown in FIG. 6B, the transparent film 11 in which the base layer 28 exists only on the inner surface of the recess 11c can be obtained.
- the transparent film 11 in which the base layer 28 exists only on the inner surface of the recess 11c obtained as described above is immersed in a known plating catalyst solution.
- a transparent film (a precursor of a transparent film for plating) in which metal ions (for example, palladium ions) as a plating catalyst are supported only inside the recess 11c is obtained.
- the plating catalyst solution a palladium (II) chloride solution or a gold (III) tetrachloride solution can be used.
- a transparent film (transparent film for plating) in which a plating catalyst such as palladium is attached only to the inner surface of the recess 11c can be obtained.
- the pattern A shown in FIG. 2 is used as the lattice pattern (lattice-like pattern) formed by the conductive portion 13, but the present embodiment is not limited to this.
- a pattern in which a plurality of straight lines (conductive parts 13) intersect at predetermined intervals in a plan view can be used as a lattice pattern.
- the planar shape of each lattice is rectangular, but the first interval P1 and the second interval P2 may be equal.
- the planar shape of each grid is square.
- the first conductive portions 13A are arranged at the first interval P1 at equal intervals, but the lattice pattern of the present embodiment is not limited to this.
- the first double-track portion 13AW may be formed by the plurality of first conductive portions 13A.
- the two adjacent first double-track portions 13AW are arranged at the first interval P1.
- the plurality of first conductive portions 13A are arranged at a fourth interval P4 narrower than the first interval P1.
- the fourth interval P4 may be, for example, 0.2 to 20 ⁇ m, 0.3 to 15 ⁇ m, or 0.5 to 10 ⁇ m.
- the first double-track portion 13AW is composed of three (three) first conductive portions 13A, but this modification is not limited to this.
- the number of the first conductive portions 13A constituting the first double-track portion 13AW may be, for example, 2 to 10, 2 to 5, or 2 to 3.
- the fourth interval P4 is a distance in a direction perpendicular to the first direction, and is a distance between opposite edges (ends) of two adjacent first conductive portions 13A in the first double-track portion 13AW. ..
- the second double-track portion 13BW may be formed by the plurality of second conductive portions 13B.
- the two adjacent second double-track portions 13BW are arranged at a second interval P2 in the first direction.
- the plurality of second conductive portions 13B are arranged at a fifth interval P5 narrower than the second interval P2 in the first direction.
- the fifth interval P5 may be, for example, 0.5 to 20 ⁇ m, 0.7 to 15 ⁇ m, or 1.0 to 10 ⁇ m.
- the second double-track portion 13BW is composed of three (three) second conductive portions 13B, but this modification is not limited to this.
- the number of the second conductive portions 13B constituting the second double-track portion 13BW may be, for example, 2 to 10, 2 to 5, or 2 to 3.
- the fifth interval P5 is a distance in the first direction, and is a distance between opposite edges (ends) of two adjacent second conductive portions 13B in the second double-track portion 13BW.
- the line width W of the conductive portion 13 May be made smaller (narrower).
- the transparency (transmittance) of the heat generating film 10 can be further improved, and the bone appearance of the conductive portion 13 can be further suppressed.
- the first double-track portion 13AW and the second double-track portion 13BW are composed of a plurality of conductive portions 13 (first conductive portion 13A, second conductive portion 13B).
- the heat-generating film 10 can obtain a sufficient amount of heat generation.
- the line width W of the conductive portion 13 may be, for example, 0.2 to 10 ⁇ m, preferably 0.3 to 5 ⁇ m, or 0.5 to 3 ⁇ m.
- the lattice pattern of the present embodiment does not have to be orthogonal to the first direction and the second direction as in the pattern E shown in FIG.
- the shape of the grid in pattern E is a parallelogram.
- the pattern E by bringing (tilting) the second direction, which is the extending direction of the second conductive portion 13B, to the first direction, a local portion applied to the intersection where the conductive wiring intersects when stress such as tension is applied. The stress can be relieved.
- Example 1 ⁇ Transparent film preparation process> As the mold 20, a Si wafer (300 mm ⁇ 300 mm) in which a lattice pattern (pattern A) shown in FIG. 2 is formed by linear convex portions having a rectangular cross-sectional shape (height 2 ⁇ m, width 1 ⁇ m) on one surface. was prepared (see FIG. 5 (a)). On the Si wafer surface, the distance between adjacent convex portions in the second direction (corresponding to the first distance P1) is 100 ⁇ m, and the distance between adjacent convex parts in the first direction (corresponding to the second distance P2) is 5000 ⁇ m. And said.
- the distance between the convex portions is the distance between the opposite edges (ends) of the two adjacent convex portions in the first direction or the second direction.
- a mold release treatment was performed by forming a film of a fluorine-based precision mold release agent (an ultrathin film having a film thickness of about 30 nm) on the surface having a convex portion.
- UV curable resin An acrylic UV curable resin (hereinafter, sometimes simply referred to as "UV curable resin”) is drop cast on the surface of the mold 20 that has been subjected to the mold release treatment to form a coating layer 22 made of the UV curable resin having a thickness of 13 ⁇ m. did.
- a PET film transparent support base material 33
- the coating layer 22 uncured transparent resin layer 12 made of UV curable resin is molded into the mold 20 and the PET film 33. It was made into a laminated body sandwiched between and (see FIG. 5 (b)).
- the laminate was irradiated with UV light having a center wavelength of 365 nm from the PET film 33 side using a high-pressure mercury lamp at 2000 mJ / cm 2 , and the UV curable resin forming the coating layer 22 was cured to cure the transparent resin layer. 12 (thickness 10 ⁇ m) was formed.
- the mold 20 was peeled off from the transparent resin layer 22 of the laminated body to obtain a transparent film 11 provided with the transparent resin layer 22 in which lattice-shaped concave portions derived from the pattern shape of the convex portion of the mold 20 were formed on the surface. (See FIG. 5 (c)).
- the distance between adjacent recesses in the second direction (corresponding to the first gap P1) is 100 ⁇ m, and the distance between the adjacent recesses in the first direction (corresponding to the second gap P2) is 100 ⁇ m. It was 5000 ⁇ m.
- the base layer raw material solution used for the silane coupling treatment was prepared as follows. 1 mL of 3-aminopropyltriethoxysilane is added to 200 mL of ethanol, and the mixture is stirred for 30 minutes to prepare a solution of 3-aminopropyltriethoxysilane (base layer raw material solution) (solvent: ethanol, concentration of 3-aminopropyltriethoxysilane). : 0.5% by volume).
- the entire surface of the transparent resin layer 12 side surface of the transparent film 11 obtained as described above was irradiated with UV light at 3000 mJ / cm 2 , and the surface of the transparent resin layer 12 was modified in advance.
- the base layer raw material solution was applied to the surface of the transparent film 11 after the surface modification on the transparent resin layer 12 side so that the film thickness (Wet film thickness) was 10 ⁇ m.
- a layer (28) composed of a reaction product with the hydroxyl group of the above was formed.
- the transparent film 11 is heated at 70 ° C. so that the layer (underlayer 28) made of 3-aminopropyltriethoxysilane is more sufficiently adhered to the surface of the transparent film 11 on the transparent resin layer 12 side and the inner surface of the recess 11c.
- the film was heat-treated for 3 minutes in a heated oven. In this way, a transparent film 11 having a base layer 28 made of 3-aminopropyltriethoxysilane formed over the entire surface of the transparent film 11 on the transparent resin layer 12 side and the inner surface of the recess 11c was obtained. (See FIG. 6 (a)).
- the entire surface of the transparent film 11 on which the base layer 28 was formed on the base layer 28 side was irradiated with UV light.
- the base layer 28 existing near the surface of the transparent film 11 was removed.
- the base layer exists on the inner surface except the vicinity of the surface of the transparent film 11. That is, a transparent film 11 in which the base layer 28 was selectively formed only on the inner surface of the recess 11c of the transparent film 11 was obtained (see FIG. 6B).
- ⁇ Catalyst selective loading process inside the recess> As a plating catalyst solution, 1.0 mL of hydrochloric acid was added to 0.2 g of palladium (II) chloride, heated to dissolve it, and then 1 L of ion-exchanged water was added to obtain a solution of palladium (II) chloride. Next, the transparent film 11 having the base layer 28 formed only on the inner surface of the recess 11c obtained as described above is immersed in the obtained plating catalyst solution for 10 minutes under room temperature conditions to form the recess 11c. A precursor of a transparent film for plating in which palladium ions were supported only on the base layer 28 formed on the inner surface was obtained.
- Electroless plating solution electroless copper plating solution having the following composition was prepared.
- Copper sulfate pentahydrate (as Cu 2+ ): 0.03 mol / L
- Formaldehyde 0.2 mol / L
- EDTA 0.24 mol / L
- Polyethylene glycol 100 ppm
- 2,2'-bipyridyl 10 ppm
- Sodium hydroxide Addition amount that makes the pH 12.5 to 13.2 Residual: Ion-exchanged water
- the transparent film 11 for plating was immersed in an electroless plating solution in a plating bath, and electroless plating was performed under the conditions of temperature: 60 ° C. and time: 10 minutes. Then, it was washed with pure water and dried. A copper plating film was formed only inside the recess 11c of the transparent film 11 for plating. In this way, a heat-generating film 10 in which a metal conductive layer (conductive portion 13) made of copper was formed inside the recess 11c was obtained (see FIG. 6C).
- the height H of the conductive portion was substantially the same as the depth D of the recess of the transparent film.
- Examples 2 to 10 A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 1 are formed on the transparent film. Changed.
- Example 11 The heat-generating film was formed by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed, and the electroless plating solution was changed to form a conductive portion by electroless nickel plating. Manufactured. The spacing between the convex portions in the first direction and the second direction of the Si wafer and the cross-sectional shape (height and width) of the convex portions were changed so that the patterns of the sizes shown in Table 1 were formed on the transparent film. For electroless plating, electroless plating was performed using an electroless plating solution (electroless nickel plating solution, pH range: 5.0 to 5.5) having the following composition (temperature: 50 ° C., time: 5). Minutes).
- electroless plating solution electroless nickel plating solution, pH range: 5.0 to 5.5
- Nickel sulfate hexahydrate (as Ni 2+ ): 0.10 mol / L Ammonium acetate: 0.40 mol / L Hydrate to sodium dihydrogen phosphate: 0.20 mol / L Residual: Ion-exchanged water
- Example 12 As the mold, the same as in Example 1 except that a Si wafer (300 mm ⁇ 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. was adjusted. Further, in the pattern D1, the number of the first conductive portions 13A constituting the first double-track portion 13AW was set to 3 (3), and the fourth interval P4 was set to 10 ⁇ m.
- Example 13 As the mold, a Si wafer (300 mm ⁇ 300 mm) in which the pattern D2 shown in FIG. 7 (b) is formed by a linear convex portion having a rectangular cross section on one surface is used, as in the first embodiment. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. was adjusted. Further, in the pattern D2, the number of the second conductive portions 13B constituting the second double-track portion 13BW was set to 3 (lines), and the fifth interval P5 was set to 10 ⁇ m.
- Example 14 and 15 A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Changed.
- Example 16 As the mold, the same as in Example 1 except that a Si wafer (300 mm ⁇ 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. was adjusted. Further, in the pattern D1, the number of the first conductive portions 13A constituting the first double-track portion 13AW was 10 (10), and the fourth interval P4 was 2 ⁇ m.
- a heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed.
- Example 3 The same method as in Example 1 except that a Si wafer (300 mm ⁇ 300 mm) in which the pattern F shown in FIG. 9 is formed by a linear convex portion having a rectangular cross section on one surface is used as a mold. Manufactured a heat-generating film.
- the pattern F is a so-called line / space (L / S) pattern, in which a line (conductive portion) extending in the first direction and having the line width and height shown in Table 3 is represented by a space (first interval) shown in Table 3. It was arranged in P1).
- Example 10 having a slightly large line width of 7 ⁇ m
- the bone visibility of the conductive portion was slightly conspicuous as compared with other Examples having a line width of 1 to 3 ⁇ m (bone appearance evaluation result: ⁇ ). ..
- Examples 1 to 11, 14 and 15 using the same pattern A as the lattice pattern are compared.
- the line width W of the conductive portion is 2 ⁇ m or less
- the first interval P1 is less than 300 ⁇ m
- the second interval P2 is 1000 to 5000 ⁇ m or less
- the bones of the conductive portion are visible. It was more suppressed (bone appearance evaluation result: ⁇ ), and the transmittance was also high.
- Comparative Example 1 since the first interval P1 was as large as 1498 ⁇ m and the number of intersections was as small as 13 / cm 2 , the area affected by disconnection was as large as 7.5 mm 2. From this result, it was found that the heat-generating film of Comparative Example 1 was easily affected by the disconnection of the conductive portion and had low durability and reliability. In Comparative Example 2, since the line width of the conductive portion was as large as 15 ⁇ m, the bone visibility was remarkable (bone visibility evaluation result: ⁇ ). In Comparative Example 3, the line width was as large as 55 ⁇ m, and since it was an L / S pattern (pattern F), there were no intersections, and the area affected by disconnection was as large as 728 mm 2.
- the heat-generating film of Comparative Example 3 had remarkable bone visibility (bone visibility evaluation result: ⁇ ), was easily affected by disconnection of the conductive portion, and had low durability and reliability. Further, in Comparative Example 4, although it was an L / S pattern, the bone visibility could be suppressed because the line width was narrow (bone visibility evaluation: ⁇ ), but there was no intersection and the area affected by the disconnection was as large as 15 mm 2. It was found that it was easily affected by the disconnection of the conductive part and had low durability and reliability.
- the heating rate of the heat-generating films obtained in Examples 6 and 7 and Comparative Example 4 was measured by the following method.
- a linear electrode having a length of 10 cm was formed of silver paste on the end surface of a heat-generating film (sample) cut into 10 cm squares as a connection electrode for passing an electric current in the first direction.
- the connection electrodes were arranged at intervals of about 10 cm.
- the heat-generating film (sample) was placed in a constant temperature bath at ⁇ 10 ° C., and a voltage of 5 V was applied between the connection electrodes for 40 seconds.
- the temperature of the sample before and after applying the voltage was measured by a thermocouple attached to the sample.
- the temperature difference (rising temperature) before and after applying the voltage of the heat-generating film was divided by the application time of 40 seconds to obtain the heating rate of the heat-generating film.
- the heating rate of the heat-generating film of Example 6 was 0.07 ° C./sec.
- the heating rate of the heat-generating film of Example 7 was 0.04 ° C./sec.
- the heat-generating film of the present invention can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generation when energized. Therefore, it can be used as a heat-generating film that can efficiently heat the windows, mirrors, etc. of the vehicle without deteriorating the visibility of the driver of the vehicle and the design of the vehicle.
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Abstract
Provided is a heat-generating film that has less visible electrically conductive portions, has high transparency (transmittance), and is capable of generating a sufficient amount of heat when energized. The heat-generating film is provided in a surface thereof with a plurality of first grooves extending in a first direction, a transparent film having a plurality of second grooves extending in a second direction across the first direction, and electrically conductive portions present in the first and second grooves. The electrically conductive portions have a line width of 0.2 to 10 μm and a height of 0.5 to 10 μm. The interval between the electrically conductive portions present in two of the first grooves adjacent to each other is 20 to 1000 μm. The number of intersecting points of the electrically conductive portions present in the first grooves and the electrically conductive portions present in the second grooves is 20 to 2500 per cm2. The area ratio of the electrically conductive portions is 0.1 to 10%.
Description
本発明は、発熱フィルム及び発熱フィルムの製造方法に関する。
The present invention relates to a heat-generating film and a method for producing a heat-generating film.
自動車等の車両には、運転中の運転者の視界を良好に維持するために窓やミラーに曇り、霜、水滴等の付着防止機構が設けられる場合がある。例えば、自動車のリアウィンドウには、リアウィンドウのガラスにプリントされた電熱線からなるデフォッガーが設けられる。デフォッガーの電熱線によりガラスを温めることで、リアウィンドウの曇り、霜を除去できる（例えば、特許文献１）。また、例えば、自動車のサイドミラーの背面（裏側）には、サイドミラーを温めて水滴の付着を防止するヒーターが設けられる（例えば、特許文献２）。
Vehicles such as automobiles may be provided with a mechanism to prevent adhesion of fogging, frost, water droplets, etc. on windows and mirrors in order to maintain good visibility of the driver while driving. For example, the rear window of an automobile is provided with a defogger consisting of a heating wire printed on the glass of the rear window. By heating the glass with a defogger heating wire, fogging and frost on the rear window can be removed (for example, Patent Document 1). Further, for example, on the back surface (back side) of the side mirror of an automobile, a heater for heating the side mirror to prevent water droplets from adhering is provided (for example, Patent Document 2).
しかし、デフォッガーは電熱線が視認され、所謂、「骨見え」が生じる。このため、車両の運転者の視界は妨げられ、また、車両の意匠性も低下する。サイドミラーに設けられるヒーターはミラーの背面に設けられているため、車両の運転者の視界や車両の意匠性に影響を与えないが、ミラーの加熱効率が低くなる。加熱効率を改良するためにヒーターをサイドミラーの前面に設けることは、車両の運転者の視界を損ね、車両の意匠性を低下させるため望ましくない。
However, the heating wire is visually recognized in the defogger, and so-called "bone visibility" occurs. For this reason, the view of the driver of the vehicle is obstructed, and the design of the vehicle is also deteriorated. Since the heater provided on the side mirror is provided on the back surface of the mirror, it does not affect the view of the driver of the vehicle or the design of the vehicle, but the heating efficiency of the mirror is lowered. It is not desirable to provide a heater in front of the side mirrors in order to improve the heating efficiency because it impairs the view of the driver of the vehicle and deteriorates the design of the vehicle.
本発明は、上記課題を解決するものであり、車両の運転者の視界及び車両の意匠性を維持しつつ、車両の窓、ミラー等を効率的に加熱できる発熱フィルムを提供する。
The present invention solves the above problems, and provides a heat-generating film capable of efficiently heating vehicle windows, mirrors, etc. while maintaining the visibility of the vehicle driver and the design of the vehicle.
第１の態様に従えば、発熱フィルムであって、表面に第１方向に延在する複数の第１溝と、第１方向と交差する第２方向に延在する複数の第２溝とを有する透明フィルムと、第１及び第２の溝内に存在する導電部とを備え、前記導電部の線幅が０．２～１０μｍであり、前記導電部の高さが、０．５～１０μｍであり、隣り合う２つの第１溝内に存在する前記導電部間の間隔が、２０～１０００μｍであり、第１溝内に存在する前記導電部と、第２溝内に存在する前記導電部との交点の数が、２０～２５００個／ｃｍ２であり、前記導電部の面積比率が０．１～１０％である発熱フィルムが提供される。
According to the first aspect, the heat-generating film has a plurality of first grooves extending in the first direction on the surface and a plurality of second grooves extending in the second direction intersecting the first direction. It is provided with a transparent film having a transparent film and conductive portions existing in the first and second grooves, the line width of the conductive portion is 0.2 to 10 μm, and the height of the conductive portion is 0.5 to 10 μm. The distance between the conductive portions existing in the two adjacent first grooves is 20 to 1000 μm, and the conductive portion existing in the first groove and the conductive portion existing in the second groove. Provided is a heat-generating film in which the number of intersections with and is 20 to 2500 / cm 2 , and the area ratio of the conductive portion is 0.1 to 10%.
前記発熱フィルムの、波長５５０ｎｍにおける光の透過率が、６０～９８％であってもよい。前記発熱フィルムの面抵抗値が０．００３～７０Ω／ｓｑ．であってもよい。第１方向における、隣り合う２つの第２溝内に存在する前記導電部間の間隔が１０００～１５０００μｍであってもよい。第２方向が第１方向と直交してもよい。
The light transmittance of the heat-generating film at a wavelength of 550 nm may be 60 to 98%. The surface resistance value of the heat-generating film is 0.003 to 70 Ω / sq. It may be. The distance between the conductive portions existing in the two adjacent second grooves in the first direction may be 1000 to 15000 μm. The second direction may be orthogonal to the first direction.
複数の第１溝内に存在する導電部から構成される第１複線部を複数備え、隣り合う２つの第１複線部は、２０～１０００μｍの第１間隔で配置され、第１複線部を構成する前記複数の導電部は、第１間隔より小さい第４間隔で配置されていてもよい。第４間隔が、０．２～２０μｍであってもよい。
A plurality of first double-track portions composed of conductive portions existing in a plurality of first grooves are provided, and two adjacent first double-track portions are arranged at a first interval of 20 to 1000 μm to form a first double-track portion. The plurality of conductive portions may be arranged at a fourth interval smaller than the first interval. The fourth interval may be 0.2 to 20 μm.
複数の第２溝内に存在する導電部から構成される第２複線部を複数備え、隣り合う２つの第２複線部は、第１方向において第２間隔で配置され、第２複線部を構成する前記複数の導電部は、第１方向において第２間隔より小さい第５間隔で配置されていてもよい。第５間隔が、０．５～２０μｍであってもよい。
A plurality of second double-track portions composed of conductive portions existing in the plurality of second grooves are provided, and two adjacent second double-track portions are arranged at a second interval in the first direction to form a second double-track portion. The plurality of conductive portions may be arranged at a fifth interval smaller than the second interval in the first direction. The fifth interval may be 0.5 to 20 μm.
第２の態様に従えば、第１の態様の発熱フィルムの製造方法であって、表面に、第１溝及び第２溝を有する前記透明フィルムを用意することと、第１溝及び第２溝に導電性材料を充填して、前記導電部を形成することとを含む発熱フィルムの製造方法が提供される。
According to the second aspect, in the method for producing a heat-generating film of the first aspect, the transparent film having the first groove and the second groove is prepared on the surface, and the first groove and the second groove are formed. Provided is a method for producing a heat-generating film, which comprises filling the film with a conductive material to form the conductive portion.
前記透明フィルムを用意することが、前記導電部に対応する凹凸パターンを有するモールドを用いたインプリントにより、前記透明フィルム上に第１溝及び第２溝を形成することを含んでもよい。前記透明フィルムが、透明支持基材と、透明支持基材上に形成された透明樹脂層とを有し、前記透明フィルムを用意することが、前記導電部に対応する凹凸パターンを有する前記モールドを用意することと、前記モールドの前記凹凸パターンが形成された表面に、光硬化性の樹脂を塗布して塗布層を形成することと、前記塗布層上に、前記透明支持基材を配置することと、前記透明支持基材側から紫外線の光を照射して前記塗布層を硬化させ、前記透明樹脂層を形成することと、前記透明樹脂層から前記モールドを剥離することとを含んでもよい。無電解メッキにより前記導電部を形成してもよい。
Preparing the transparent film may include forming a first groove and a second groove on the transparent film by imprinting using a mold having a concavo-convex pattern corresponding to the conductive portion. The transparent film has a transparent support base material and a transparent resin layer formed on the transparent support base material, and preparing the transparent film provides the mold having an uneven pattern corresponding to the conductive portion. To prepare, to apply a photocurable resin to the surface of the mold on which the uneven pattern is formed to form a coating layer, and to arrange the transparent support base material on the coating layer. And, the coating layer may be cured by irradiating the transparent support base material side with ultraviolet light to form the transparent resin layer, and the mold may be peeled off from the transparent resin layer. The conductive portion may be formed by electroless plating.
本発明の発熱フィルムは、導電部の骨見えを抑制でき、透明性（透過率）が高く、また、通電時に十分な発熱量を得られる。このため、車両の運転者の視界及び車両の意匠性を維持しつつ、車両の窓、ミラー等を効率的に加熱できる発熱フィルムとして利用できる。また、本発明の発熱フィルムは導電部の断線の影響を受け難く、耐久性及び信頼性が高い。
The heat-generating film of the present invention can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generation when energized. Therefore, it can be used as a heat-generating film that can efficiently heat the windows, mirrors, etc. of the vehicle while maintaining the visibility of the driver of the vehicle and the design of the vehicle. In addition, the heat-generating film of the present invention is not easily affected by disconnection of the conductive portion, and has high durability and reliability.
以下、本発明の発熱フィルム及びその製造方法の実施形態について、図面を参照しながら説明する。
Hereinafter, embodiments of the heat-generating film of the present invention and the method for producing the same will be described with reference to the drawings.
［発熱フィルム］
本実施形態の発熱フィルム１０は、図１（ａ）に示すように、透明支持基材３３及びその上に形成された透明樹脂層１２から構成される透明フィルム１１と、透明フィルム１１上に形成された導電部１３とを備える。透明樹脂層１２は断面が矩形の凹部（溝）１１ｃを有する。凹部１１ｃは、図２に示すように、透明フィルム１１の表面１１ｓにおいて、第１方向に延在する第１溝１１Ａと、第１方向と交差する第２方向に延在する第２溝１１Ｂを含む。第１溝１１Ａと第２溝１１Ｂを含む凹部（溝）１１ｃは、発熱フィルム１０の平面視で格子状のパターン（パターンＡ）を形成する格子溝である。パターンＡでは、第１方向と第２方向とが直交している。導電部１３は、透明フィルム１１の凹部１１ｃ内に導電性材料が充填されてなる。即ち、導電部１３は、凹部１１ｃ内に存在する。導電部１３は、第１溝１１Ａに充填された第１導電部１３Ａと、第２溝１１Ｂに充填された第２導電部１３Ｂを含む。図２に示すように、第１導電部１３Ａ及び第２導電部１３Ｂは格子状であり、透明フィルム１１の表面１１ａに格子状のパターン（パターンＡ）を形成する。尚、第１溝１１Ａと第２溝１１Ｂとを区別する必要がないときは、これらをまとめて指して凹部（溝、格子溝）１１ｃと記載する。同様に、第１導電部１３Ａと第２導電部１３Ｂとを区別する必要がないときは、これらをまとめて指して、導電部１３と記載する。 [Heat-generating film]
As shown in FIG. 1A, the heat-generatingfilm 10 of the present embodiment is formed on a transparent film 11 composed of a transparent support base material 33 and a transparent resin layer 12 formed on the transparent support base material 33, and on the transparent film 11. The conductive portion 13 is provided. The transparent resin layer 12 has a recess (groove) 11c having a rectangular cross section. As shown in FIG. 2, the recess 11c has a first groove 11A extending in the first direction and a second groove 11B extending in the second direction intersecting the first direction on the surface 11s of the transparent film 11. include. The recess (groove) 11c including the first groove 11A and the second groove 11B is a lattice groove that forms a grid-like pattern (pattern A) in a plan view of the heat generating film 10. In pattern A, the first direction and the second direction are orthogonal to each other. The conductive portion 13 is formed by filling the recess 11c of the transparent film 11 with a conductive material. That is, the conductive portion 13 exists in the recess 11c. The conductive portion 13 includes a first conductive portion 13A filled in the first groove 11A and a second conductive portion 13B filled in the second groove 11B. As shown in FIG. 2, the first conductive portion 13A and the second conductive portion 13B are in a grid pattern, and a grid pattern (pattern A) is formed on the surface 11a of the transparent film 11. When it is not necessary to distinguish between the first groove 11A and the second groove 11B, these are collectively referred to as a recess (groove, lattice groove) 11c. Similarly, when it is not necessary to distinguish between the first conductive portion 13A and the second conductive portion 13B, these are collectively referred to as the conductive portion 13.
本実施形態の発熱フィルム１０は、図１（ａ）に示すように、透明支持基材３３及びその上に形成された透明樹脂層１２から構成される透明フィルム１１と、透明フィルム１１上に形成された導電部１３とを備える。透明樹脂層１２は断面が矩形の凹部（溝）１１ｃを有する。凹部１１ｃは、図２に示すように、透明フィルム１１の表面１１ｓにおいて、第１方向に延在する第１溝１１Ａと、第１方向と交差する第２方向に延在する第２溝１１Ｂを含む。第１溝１１Ａと第２溝１１Ｂを含む凹部（溝）１１ｃは、発熱フィルム１０の平面視で格子状のパターン（パターンＡ）を形成する格子溝である。パターンＡでは、第１方向と第２方向とが直交している。導電部１３は、透明フィルム１１の凹部１１ｃ内に導電性材料が充填されてなる。即ち、導電部１３は、凹部１１ｃ内に存在する。導電部１３は、第１溝１１Ａに充填された第１導電部１３Ａと、第２溝１１Ｂに充填された第２導電部１３Ｂを含む。図２に示すように、第１導電部１３Ａ及び第２導電部１３Ｂは格子状であり、透明フィルム１１の表面１１ａに格子状のパターン（パターンＡ）を形成する。尚、第１溝１１Ａと第２溝１１Ｂとを区別する必要がないときは、これらをまとめて指して凹部（溝、格子溝）１１ｃと記載する。同様に、第１導電部１３Ａと第２導電部１３Ｂとを区別する必要がないときは、これらをまとめて指して、導電部１３と記載する。 [Heat-generating film]
As shown in FIG. 1A, the heat-generating
＜透明フィルム＞
透明フィルム１１は、前述のように、透明支持基材３３とその上に積層された透明樹脂層１２を有する。 <Transparent film>
As described above, thetransparent film 11 has a transparent support base material 33 and a transparent resin layer 12 laminated on the transparent support base material 33.
透明フィルム１１は、前述のように、透明支持基材３３とその上に積層された透明樹脂層１２を有する。 <Transparent film>
As described above, the
透明樹脂層１２としては、光硬化および熱硬化、湿気硬化型、化学硬化型（二液混合）等の樹脂を用いることができる。具体的には、例えば、エポキシ系、アクリル系、メタクリル系、ビニルエーテル系、オキセタン系、ウレタン系、メラミン系、ウレア系、ポリエステル系、ポリオレフィン系、フェノール系、架橋型液晶系、フッ素系、シリコーン系、ポリアミド系等のモノマー、オリゴマー、ポリマー等の各種樹脂が挙げられる。透明樹脂層１２の厚さは０．５～５００μｍ、１～４００μｍ、５～２００μｍ、又は２～２０μｍの範囲内であってよい。厚さが前記下限未満では、透明樹脂層１２に形成される凹部１１ｃの深さが不十分となり易く、前記上限を超えると、硬化時に生じる樹脂の体積変化の影響が大きくなる懸念がある。
As the transparent resin layer 12, resins such as photocurable, thermosetting, moisture-curable, and chemically curable (two-component mixture) can be used. Specifically, for example, epoxy-based, acrylic-based, methacrylic-based, vinyl ether-based, oxetane-based, urethane-based, melamine-based, urea-based, polyester-based, polyolefin-based, phenol-based, crosslinked liquid crystal-based, fluorine-based, and silicone-based. , Polyamide-based monomers, oligomers, polymers and other various resins. The thickness of the transparent resin layer 12 may be in the range of 0.5 to 500 μm, 1 to 400 μm, 5 to 200 μm, or 2 to 20 μm. If the thickness is less than the lower limit, the depth of the recess 11c formed in the transparent resin layer 12 tends to be insufficient, and if the thickness exceeds the upper limit, there is a concern that the influence of the volume change of the resin that occurs during curing becomes large.
透明支持基材３３としては、可視光を透過する公知のフィルム基材を利用することができる。例えば、ガラス等の透明無機材料からなる基材；ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート等）、（メタ）アクリル系樹脂（ポリメチルメタクリレート等）、ポリカーボネート、ポリ塩化ビニル、スチレン系樹脂（ＡＢＳ樹脂等）、セルロース系樹脂（トリアセチルセルロース等）、ポリイミド系樹脂（ポリイミド樹脂、ポリイミドアミド樹脂等）、シクロオレフィンポリマー等の樹脂からなる基材などを利用することができる。可撓性の観点から、透明支持基材３３は樹脂フィルムであってよい。透明支持基材３３の厚さは、光学特性の観点から１～５００μｍ、１０～３００μｍ、又は２０～１５０μｍであることが好ましい。１μｍよりも薄い場合は支持基材としての機能が損なわれる恐れがあり、５００μｍよりも厚い場合は光透過性が十分でない場合がある。
As the transparent support base material 33, a known film base material that transmits visible light can be used. For example, a base material made of a transparent inorganic material such as glass; polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.), (meth) acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, etc. A substrate made of a resin such as a styrene resin (ABS resin or the like), a cellulose resin (triacetyl cellulose or the like), a polyimide resin (polyimide resin, a polyimide amide resin or the like), a cycloolefin polymer or the like can be used. From the viewpoint of flexibility, the transparent support base material 33 may be a resin film. The thickness of the transparent support base material 33 is preferably 1 to 500 μm, 10 to 300 μm, or 20 to 150 μm from the viewpoint of optical characteristics. If it is thinner than 1 μm, the function as a supporting base material may be impaired, and if it is thicker than 500 μm, the light transmission may not be sufficient.
＜導電部＞
導電部１３は、通電されることにより発熱する。したがって、導電部１３は、発熱フィルム１０の発熱部である。図１（ｂ）に示すように、導電部１３は、透明フィルム１１の凹部(溝)１１ｃを充填するように形成されており、凹部１１ｃのフィルムの面内方向の外側にはみ出てはいない。本実施形態では導電部１３の上面１３ｓ(溝から露出している部分)と透明フィルム１１の表面１１ｓの間には段差がなく、両者は同一平面内に位置している。すなわち、凹部１１ｃの深さＤと導電部１３の高さＨは略同一である。尚、透明フィルム１１の表面１１ｓとは、透明フィルム１１の凹部１１ｃを除く表面部分を意味する。 <Conductive part>
Theconductive portion 13 generates heat when energized. Therefore, the conductive portion 13 is a heat generating portion of the heat generating film 10. As shown in FIG. 1B, the conductive portion 13 is formed so as to fill the recess (groove) 11c of the transparent film 11, and does not protrude outside the film of the recess 11c in the in-plane direction. In the present embodiment, there is no step between the upper surface 13s of the conductive portion 13 (the portion exposed from the groove) and the surface 11s of the transparent film 11, and both are located in the same plane. That is, the depth D of the recess 11c and the height H of the conductive portion 13 are substantially the same. The surface 11s of the transparent film 11 means a surface portion of the transparent film 11 excluding the recess 11c.
導電部１３は、通電されることにより発熱する。したがって、導電部１３は、発熱フィルム１０の発熱部である。図１（ｂ）に示すように、導電部１３は、透明フィルム１１の凹部(溝)１１ｃを充填するように形成されており、凹部１１ｃのフィルムの面内方向の外側にはみ出てはいない。本実施形態では導電部１３の上面１３ｓ(溝から露出している部分)と透明フィルム１１の表面１１ｓの間には段差がなく、両者は同一平面内に位置している。すなわち、凹部１１ｃの深さＤと導電部１３の高さＨは略同一である。尚、透明フィルム１１の表面１１ｓとは、透明フィルム１１の凹部１１ｃを除く表面部分を意味する。 <Conductive part>
The
導電部１３の線幅Ｗは、０．２～１０μｍであり、好ましくは、０．５～１０μｍ、０．７～８μｍ、０．９～６μｍ、又は１～５μｍである。導電部１３の線幅Ｗが上記範囲の上限を超えると、導電部１３が視認可能になり、骨見えが生じ、発熱フィルム１０の透明性（透過率）が低下する虞がある。また、導電部１３の線幅Ｗが上記範囲の下限未満であると、導電性が不十分になり発熱量が不足する虞がある。また、導電部１３が断線するリスクが高まり、発熱フィルム１０の耐久性及び信頼性が低下する。尚、導電部１３の線幅Ｗは、導電部１３が延在する方向と垂直な断面における導電部１３の幅の最大値である。本実施形態では、第１導電部１３Ａと、第２導電部１３Ｂとは、同一の線幅Ｗを有する。しかし、本実施形態はこれに限定されず、第１導電部１３Ａ及び第２導電部１３Ｂは、それぞれ異なる線幅Ｗを有してよい。
The line width W of the conductive portion 13 is 0.2 to 10 μm, preferably 0.5 to 10 μm, 0.7 to 8 μm, 0.9 to 6 μm, or 1 to 5 μm. If the line width W of the conductive portion 13 exceeds the upper limit of the above range, the conductive portion 13 becomes visible, bones are visible, and the transparency (transmittance) of the heat-generating film 10 may decrease. Further, if the line width W of the conductive portion 13 is less than the lower limit of the above range, the conductivity may be insufficient and the amount of heat generated may be insufficient. In addition, the risk of disconnection of the conductive portion 13 increases, and the durability and reliability of the heat generating film 10 decrease. The line width W of the conductive portion 13 is the maximum value of the width of the conductive portion 13 in the cross section perpendicular to the direction in which the conductive portion 13 extends. In the present embodiment, the first conductive portion 13A and the second conductive portion 13B have the same line width W. However, the present embodiment is not limited to this, and the first conductive portion 13A and the second conductive portion 13B may have different line widths W.
導電部１３の高さＨは、０．５～１０μｍであり、好ましくは、０．７～７μｍ、１～５μｍ又は２～４μｍである。導電部１３の高さＨが上記範囲の上限を超えると、格子パターンを形成し難くなる。また、導電部１３の高さＨが上記範囲の下限未満であると、導電性が不十分になり発熱量が不足する虞がある。発熱フィルム１０の耐久性及び信頼性が低下する。尚、導電部１３の高さＨとは、凹部１１ｃの底から導電部１３の表面１３ｓまでの距離（導電部１３の厚さ）の最大値である。本実施形態では、第１導電部１３Ａと、第２導電部１３Ｂとは、同一の高さＨを有する。しかし、本実施形態はこれに限定されず、第１導電部１３Ａ及び第２導電部１３Ｂは、それぞれ異なる高さＨを有してよい。
The height H of the conductive portion 13 is 0.5 to 10 μm, preferably 0.7 to 7 μm, 1 to 5 μm, or 2 to 4 μm. If the height H of the conductive portion 13 exceeds the upper limit of the above range, it becomes difficult to form a lattice pattern. Further, if the height H of the conductive portion 13 is less than the lower limit of the above range, the conductivity may be insufficient and the amount of heat generated may be insufficient. The durability and reliability of the heat-generating film 10 are reduced. The height H of the conductive portion 13 is the maximum value of the distance (thickness of the conductive portion 13) from the bottom of the concave portion 11c to the surface 13s of the conductive portion 13. In the present embodiment, the first conductive portion 13A and the second conductive portion 13B have the same height H. However, the present embodiment is not limited to this, and the first conductive portion 13A and the second conductive portion 13B may have different heights H, respectively.
図１（ｂ）に示すように導電部１３の高さＨは、好ましくは、導電部１３の線幅Ｗの０．１倍以上、０．１～５倍又は０．５～２倍であってよい。すなわち、導電部１３の延在方向に垂直な面における断面形状の縦横比(アスペクト比)は好ましくは１：１０～５：１又は１：２～２：１の範囲内であってよい。本実施形態の導電部１３の高さＨが線幅Ｗの１倍以上であることにより、導電部１３は十分な導電性、発熱性を有することができる。それにより、発熱フィルム１０は骨見えのない良好な外観と高導電性を両立することができる。また、導電部１３の高さＨが線幅Ｗの５倍より大きい場合、発熱フィルム１０を斜めから見た場合に視認性が低下する虞がある。
As shown in FIG. 1B, the height H of the conductive portion 13 is preferably 0.1 times or more, 0.1 to 5 times, or 0.5 to 2 times the line width W of the conductive portion 13. You can. That is, the aspect ratio of the cross-sectional shape on the plane perpendicular to the extending direction of the conductive portion 13 may be preferably in the range of 1:10 to 5: 1 or 1: 2 to 2: 1. When the height H of the conductive portion 13 of the present embodiment is one or more times the line width W, the conductive portion 13 can have sufficient conductivity and heat generation. As a result, the heat-generating film 10 can achieve both a good appearance without bone visibility and high conductivity. Further, when the height H of the conductive portion 13 is larger than 5 times the line width W, the visibility may be lowered when the heat generating film 10 is viewed from an angle.
凹部１１ｃの深さＤと導電部１３の高さＨは、等しくなくてもよい。例えば、図３（ａ）に示すように凹部１１ｃの深さＤより導電部１３の高さＨが高くてもよい。すなわち、導電部１３の盛り上がり部１３ｘ（透明フィルム１１の表面１１ｓよりも高い部分）が、存在していてもよい。それでも、盛り上がり部１３ｘは、凹部１１ｃの基板面内方向の外側にはみ出ることはない。こうすることにより、導電部１３の断面積を大きくすることができ、この結果、格子パターンにおける導電部１３の面積比率（被覆率）を上げることなく導電部１３の抵抗値を下げることができる。盛り上がり部１３ｘの高さ（表面１１ｓからの高さ）は、０．５μｍ以下にすることが好ましい。０．５μｍを超えると導電部の耐摩耗性が低下する。凹部１１ｃの深さＤに対する導電部１３の高さＨの比（Ｈ／Ｄ）は、耐摩耗性の観点から１．０＜Ｈ／Ｄ≦１．２、１．０＜Ｈ／Ｄ≦１．１５、又は１．０＜Ｈ／Ｄ≦１．１０（但し、盛り上がり部１３ｘの高さは０．５μｍ以下）であることが好ましい。
The depth D of the recess 11c and the height H of the conductive portion 13 do not have to be equal. For example, as shown in FIG. 3A, the height H of the conductive portion 13 may be higher than the depth D of the recess 11c. That is, the raised portion 13x of the conductive portion 13 (the portion higher than the surface 11s of the transparent film 11) may be present. Even so, the raised portion 13x does not protrude to the outside of the recess 11c in the inward direction of the substrate surface. By doing so, the cross-sectional area of the conductive portion 13 can be increased, and as a result, the resistance value of the conductive portion 13 can be lowered without increasing the area ratio (coverage ratio) of the conductive portion 13 in the lattice pattern. The height of the raised portion 13x (height from the surface 11s) is preferably 0.5 μm or less. If it exceeds 0.5 μm, the wear resistance of the conductive portion decreases. The ratio (H / D) of the height H of the conductive portion 13 to the depth D of the recess 11c is 1.0 <H / D ≦ 1.2, 1.0 <H / D ≦ 1 from the viewpoint of wear resistance. It is preferably .15 or 1.0 <H / D ≦ 1.10 (however, the height of the raised portion 13x is 0.5 μm or less).
あるいは、図３（ｂ）に示すように、導電部１３が凹部１１ｃの深さより低く、導電部１３が凹部１１ｃの内部に部分的に充填されていてもよい。こうすることにより、導電部１３が凹部内に完全に収容されるために透明フィルム１１の表面の耐摩耗性に優れ、導電部１３が劣化し難くなる。凹部１１ｃの深さＤに対する導電部１３の高さＨの比（Ｈ／Ｄ）は、導電性を確保するという観点から、０．１＜Ｈ／Ｄ、０．３≦Ｈ／Ｄ、又は０．５≦Ｈ／Ｄであることが好ましい。
Alternatively, as shown in FIG. 3B, the conductive portion 13 may be lower than the depth of the recess 11c, and the conductive portion 13 may be partially filled inside the recess 11c. By doing so, since the conductive portion 13 is completely accommodated in the recess, the surface of the transparent film 11 is excellent in wear resistance, and the conductive portion 13 is less likely to deteriorate. The ratio (H / D) of the height H of the conductive portion 13 to the depth D of the recess 11c is 0.1 <H / D, 0.3 ≦ H / D, or 0 from the viewpoint of ensuring conductivity. It is preferable that .5 ≦ H / D.
本実施形態では、図２に示すように、同一の線幅Ｗ、同一の高さＨを有する複数の導電部１３（第１導電部１３Ａ及び第２導電部１３Ｂ）が規則的に格子状に交差して、透明フィルム１１の表面１１ｓ上に格子パターン（格子状のパターンＡ）を形成する。第１導電部１３Ａ及び第２導電部１３Ｂが互いに直交することにより導電部１３は平面視で均等に分散し、これにより、骨見えが抑制され、透明性が向上する。また、パターンＡは、第１導電部１３Ａと、第２導電部１３Ｂとが交差する（直交する）交点Ｒを複数有する。詳細は後述するが、パターンＡが交点Ｒを有するため、本実施形態の発熱フィルム１０は導電部１３の断線の影響を受け難く、耐久性及び信頼性が高い。
In the present embodiment, as shown in FIG. 2, a plurality of conductive portions 13 (first conductive portion 13A and second conductive portion 13B) having the same line width W and the same height H are regularly arranged in a grid pattern. They intersect to form a grid pattern (lattice pattern A) on the surface 11s of the transparent film 11. Since the first conductive portion 13A and the second conductive portion 13B are orthogonal to each other, the conductive portion 13 is evenly dispersed in a plan view, whereby the appearance of bones is suppressed and the transparency is improved. Further, the pattern A has a plurality of intersections R where the first conductive portion 13A and the second conductive portion 13B intersect (orthogonally). Although the details will be described later, since the pattern A has the intersection R, the heat-generating film 10 of the present embodiment is not easily affected by the disconnection of the conductive portion 13, and has high durability and reliability.
隣り合う２つの第１溝１１Ａに充填された導電部間の間隔、即ち、隣り合う２つの第１導電部１３Ａ間の第１間隔Ｐ１は、２０～１０００μｍであり、好ましくは、５０～８００μｍ、８０～６００μｍ又は９０～５００μｍである。第１間隔Ｐ１が上記範囲の下限未満であると、発熱フィルム１０の透明性（透過率）が低下する虞がある。また、第１間隔Ｐ１が上記範囲の上限を超えると、発熱フィルム１０の発熱量が不足する虞がある。また、交点Ｒの数が減少するため、発熱フィルム１０は導電部１３の断線の影響を受け易くなり、耐久性及び信頼性が低下する虞がある。尚、第１間隔Ｐ１は、第１方向に垂直な方向における、隣り合う２つの第１導電部１３Ａの間の距離（間隔）である。第１方向と第２方向が直交するパターンＡにおいては、第１間隔Ｐ１は、第２方向における距離（間隔）である。また、第１間隔Ｐ１は、第１方向に垂直な方向における、隣り合う２つの第１導電部１３Ａの対向する縁（端部）の間の距離である。
The distance between the conductive portions filled in the two adjacent first conductive portions 11A, that is, the first distance P1 between the two adjacent first conductive portions 13A is 20 to 1000 μm, preferably 50 to 800 μm. It is 80 to 600 μm or 90 to 500 μm. If the first interval P1 is less than the lower limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease. Further, if the first interval P1 exceeds the upper limit of the above range, the amount of heat generated by the heat generating film 10 may be insufficient. Further, since the number of intersections R is reduced, the heat generating film 10 is easily affected by the disconnection of the conductive portion 13, and the durability and reliability may be lowered. The first interval P1 is a distance (interval) between two adjacent first conductive portions 13A in a direction perpendicular to the first direction. In the pattern A in which the first direction and the second direction are orthogonal to each other, the first interval P1 is a distance (interval) in the second direction. The first interval P1 is the distance between the opposing edges (ends) of the two adjacent first conductive portions 13A in the direction perpendicular to the first direction.
第１方向における、隣り合う２つの第２溝１１Ｂに充填された導電部間の間隔、即ち、第１方向における、隣り合う２つの第２導電部１３Ｂ間の第２間隔Ｐ２は、特に限定されない。発熱フィルム１０の透明性と発熱量とを両立する観点からは、例えば、２０～２００００μｍ、５０～１５０００μｍ、８０～６０００μｍ、又は９０～３０００μｍであってよい。第２間隔Ｐ２が上記範囲であれば、高い透明性（透過率）を実現できる。また、図２に示すパターンＡにおいて、第２間隔Ｐ２は、第１間隔Ｐ１より大きい（広い）が、本実施形態はこれに限定されない。第１間隔Ｐ１と第２間隔Ｐ２とは、同一であってもよいし、異なってもよい。但し、導電部１３の骨見えを抑制し、透明性（透過率）を高める観点からは、第２間隔Ｐ２は、第１間隔Ｐ１より大きい（広い）方が好ましい。尚、第２間隔Ｐ２は、第１方向における、隣り合う２つの第２導電部１３Ｂの対向する縁（端部）の間の距離である。
The distance between the conductive portions filled in the two adjacent second conductive portions 11B in the first direction, that is, the second distance P2 between the two adjacent second conductive portions 13B in the first direction is not particularly limited. .. From the viewpoint of achieving both the transparency of the heat-generating film 10 and the amount of heat generated, it may be, for example, 20 to 20000 μm, 50 to 15000 μm, 80 to 6000 μm, or 90 to 3000 μm. When the second interval P2 is in the above range, high transparency (transmittance) can be realized. Further, in the pattern A shown in FIG. 2, the second interval P2 is larger (wider) than the first interval P1, but the present embodiment is not limited to this. The first interval P1 and the second interval P2 may be the same or different. However, from the viewpoint of suppressing the appearance of bones in the conductive portion 13 and increasing the transparency (transmittance), it is preferable that the second interval P2 is larger (wider) than the first interval P1. The second interval P2 is the distance between the opposing edges (ends) of the two adjacent second conductive portions 13B in the first direction.
第１間隔Ｐ１及び第２間隔Ｐ２は、導電部１３の線幅Ｗと共に、導電部１３の骨見えに影響を与える場合がある。導電部１３の線幅Ｗの大きさに依存するが、第１間隔Ｐ１及び第２間隔Ｐ２が小さく（狭く）なると、導電部１３の骨見えがより抑制される場合がある。これは、第１間隔Ｐ１及び第２間隔Ｐ２の大きさを人間の目が認識できなくなり、導電部１３の格子パターンがより目立たなくなるためだと推測される。例えば、導電部１３の線幅Ｗが２μｍ以下であるとき、第１間隔Ｐ１が３００μｍ未満で、且つ第２間隔Ｐ２が５０００μｍ以下であると、骨見えがより抑制されるため好ましい。更に、上述のように、第２間隔Ｐ２は狭過ぎると透明性が低下する虞があるため、第２間隔Ｐ２は、例えば、１０００以上であることが好ましい。したがって、骨見えを抑制し、且つ高い透明性を得るためには、例えば、導電部１３の線幅Ｗが２μｍ以下であるとき、第１間隔Ｐ１が３００μｍ未満で、且つ第２間隔Ｐ２が１０００～５０００μｍ以下であることが好ましい。
The first interval P1 and the second interval P2 may affect the appearance of the bone of the conductive portion 13 together with the line width W of the conductive portion 13. Although it depends on the size of the line width W of the conductive portion 13, when the first interval P1 and the second interval P2 become smaller (narrower), the bone appearance of the conductive portion 13 may be further suppressed. It is presumed that this is because the human eye cannot recognize the sizes of the first interval P1 and the second interval P2, and the lattice pattern of the conductive portion 13 becomes less noticeable. For example, when the line width W of the conductive portion 13 is 2 μm or less, it is preferable that the first interval P1 is less than 300 μm and the second interval P2 is 5000 μm or less because the appearance of bone is further suppressed. Further, as described above, if the second interval P2 is too narrow, the transparency may decrease. Therefore, the second interval P2 is preferably 1000 or more, for example. Therefore, in order to suppress the appearance of bone and obtain high transparency, for example, when the line width W of the conductive portion 13 is 2 μm or less, the first interval P1 is less than 300 μm and the second interval P2 is 1000. It is preferably about 5000 μm or less.
格子状の導電部１３における交点Ｒの数、即ち、第１溝１１Ａ内に存在する第１導電部１３Ａと、第２溝１１Ｂ内に存在する第２導電部１３Ｂとの交点Ｒの数は、２０～２５００個／ｃｍ２であり、好ましくは、３０～２０００個／ｃｍ２又は５０～１５００個／ｃｍ２である。本実施形態において、発熱部である導電部１３に断線が生じた場合、断線部の周辺には通電できず発熱できなくなり、発熱フィルム１０の表面１１ｓの一部は、発熱フィルムとしての機能できなくなる。発熱フィルム１０の表面１１ｓにおいて、１箇所の導電部１３の断線により発熱に寄与できなくなる面積を「断線影響面積」と定義する。格子パターンにおいて、交点Ｒの数が多いほど断線影響面積は小さくなる。即ち、交点Ｒの数が多いほど、発熱フィルム１０は導電部１３の断線の影響を受け難くなり、発熱フィルム１０の耐久性及び信頼性が高くなる。格子パターンにおける交点Ｒの数が上記範囲の下限未満であると、発熱フィルム１０は十分な耐久性及び信頼性を得られない。反対に、格子パターンにおける交点Ｒの数が上記範囲の上限を超えると、発熱フィルム１０の透明性（透過率）が低下する虞がある。
The number of intersections R in the grid-like conductive portion 13, that is, the number of intersections R between the first conductive portion 13A existing in the first groove 11A and the second conductive portion 13B existing in the second groove 11B is determined. It is 20 to 2500 pieces / cm 2 , preferably 30 to 2000 pieces / cm 2 or 50 to 1500 pieces / cm 2 . In the present embodiment, when the conductive portion 13 which is the heat generating portion is disconnected, the periphery of the disconnected portion cannot be energized and heat cannot be generated, and a part of the surface 11s of the heat generating film 10 cannot function as the heat generating film. .. On the surface 11s of the heat-generating film 10, the area that cannot contribute to heat generation due to the disconnection of the conductive portion 13 at one location is defined as the “disconnection-affected area”. In the grid pattern, the larger the number of intersections R, the smaller the area affected by disconnection. That is, the larger the number of intersections R, the less susceptible the heat-generating film 10 is to the disconnection of the conductive portion 13, and the higher the durability and reliability of the heat-generating film 10. If the number of intersections R in the lattice pattern is less than the lower limit of the above range, the heat-generating film 10 cannot obtain sufficient durability and reliability. On the contrary, if the number of intersections R in the lattice pattern exceeds the upper limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease.
また、導電部１３の面積比率は、０．１～１０％であり、好ましくは、０．２～３％又は０．３～１％である。導電部１３の面積比率が上記範囲の下限未満であると、発熱量が不足する虞がある。導電部１３の面積比率が上記範囲の上限を超えると、発熱フィルム１０の透明性（透過率）が低下する虞がある。尚、導電部１３の面積比率とは、発熱フィルム１０の平面視において、発熱フィルム１０の表面の格子状の導電部１３が形成されている領域（格子状のパターンＡが形成されている領域）における導電部１３の被覆率である。
The area ratio of the conductive portion 13 is 0.1 to 10%, preferably 0.2 to 3% or 0.3 to 1%. If the area ratio of the conductive portion 13 is less than the lower limit of the above range, the calorific value may be insufficient. If the area ratio of the conductive portion 13 exceeds the upper limit of the above range, the transparency (transmittance) of the heat generating film 10 may decrease. The area ratio of the conductive portion 13 is a region in which the grid-like conductive portion 13 on the surface of the heat-generating film 10 is formed (a region in which the grid-like pattern A is formed) in the plan view of the heat-generating film 10. It is the coverage of the conductive portion 13 in the above.
導電部１３の材料としては、ニッケル、銅、亜鉛、クロム、パラジウム、銀、スズ、鉛、金、アルミニウムなどの金属、並びにこれらの金属の合金や化合物等が挙げられる。導電性の観点からは、ニッケル、銅、銀、金等の金属並びにこれらの金属の合金や化合物等が好ましく、フレキシブル性の観点からは、銀、銅、ニッケル等の金属又は合金が好ましい。
Examples of the material of the conductive portion 13 include metals such as nickel, copper, zinc, chromium, palladium, silver, tin, lead, gold and aluminum, and alloys and compounds of these metals. From the viewpoint of conductivity, metals such as nickel, copper, silver and gold, and alloys and alloys of these metals are preferable, and from the viewpoint of flexibility, metals or alloys such as silver, copper and nickel are preferable.
本実施形態の発熱フィルム１０の波長５５０ｎｍの光の透過率は、好ましくは、６０～９８％、８０～９５％又は８５～９２％であってよい。透過率が上記範囲内であれば、発熱フィルム１０は十分な透明性を有する。
The light transmittance of the heat-generating film 10 of the present embodiment at a wavelength of 550 nm is preferably 60 to 98%, 80 to 95%, or 85 to 92%. When the transmittance is within the above range, the heat-generating film 10 has sufficient transparency.
本実施形態の発熱フィルム１０の面抵抗値は、好ましくは、０．００３～７０Ω／ｓｑ．、０．０５～３０Ω／ｓｑ．又は０．１～２０Ω／ｓｑ．であってよい。面抵抗値がこの範囲であれば、発熱フィルム１０は通電時に十分な発熱量を得られる。
The surface resistance value of the heat generating film 10 of the present embodiment is preferably 0.003 to 70 Ω / sq. , 0.05 to 30 Ω / sq. Or 0.1 to 20 Ω / sq. May be. When the surface resistance value is in this range, the heat generating film 10 can obtain a sufficient amount of heat generated when energized.
本実施形態の発熱フィルム１０の昇温速度は、好ましくは、０．０２～０．５℃／ｓｅｃ.、０．０３～０．４℃／ｓｅｃ.、又は０．０４～０．３℃／ｓｅｃ.であってよい。昇温速度がこの範囲であれば、発熱フィルムは通電時に十分な発熱特性を発揮できる。尚、昇温速度は、例えば、後述の実施例で説明する測定方法及び測定条件で測定できる。
The heating rate of the heat generating film 10 of the present embodiment is preferably 0.02 to 0.5 ° C./sec., 0.03 to 0.4 ° C./sec., Or 0.04 to 0.3 ° C./sec. It may be sec. When the heating rate is within this range, the heat-generating film can exhibit sufficient heat-generating characteristics when energized. The rate of temperature rise can be measured, for example, by the measurement method and measurement conditions described in Examples described later.
発熱フィルム１０は、導電部１３に通電して発熱するために、導電部１３の末端に連結する引き出し配線を備えていてもよい。引き出し配線は、導電部１３の上面１３ｓと同じ高さにしてよく、特に、導電部１３の上面１３ｓ及び透明フィルム１１ａの表面１１ｓとの間には段差がなく、いずれも同一平面内に位置してよい。引き出し配線の材料としては、導電部１３の材料として例示したものと同様のものを用いることができる。
The heat-generating film 10 may include a lead-out wiring connected to the end of the conductive portion 13 in order to energize the conductive portion 13 to generate heat. The lead-out wiring may be at the same height as the upper surface 13s of the conductive portion 13, and in particular, there is no step between the upper surface 13s of the conductive portion 13 and the surface 11s of the transparent film 11a, and both are located in the same plane. You can. As the material of the lead-out wiring, the same material as those exemplified as the material of the conductive portion 13 can be used.
以上説明したように、本実施形態の発熱フィルム１０は、第１導電部１３Ａ及び第２導電部１３Ｂの線幅Ｗ及び高さＨ、格子パターンにおける第１間隔Ｐ１、交点の数、及び導電部の面積比率が所定の範囲内である。これにより、本実施形態の発熱フィルム１０は、導電部の骨見えを抑制でき、透明性（透過率）が高く、また、通電時に十分な発熱量を得られる。更に、本実施形態の発熱フィルムは、導電部の断線の影響を受け難く、耐久性及び信頼性が高い。このため、本実施形態の発熱フィルム１０は、車両の運転者の視界及び車両の意匠性を低下させずに、車両の窓、ミラー等を効率的に加熱できる発熱フィルムとして利用できる。
As described above, in the heat generating film 10 of the present embodiment, the line width W and height H of the first conductive portion 13A and the second conductive portion 13B, the first interval P1 in the lattice pattern, the number of intersections, and the conductive portion The area ratio of is within a predetermined range. As a result, the heat-generating film 10 of the present embodiment can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generated when energized. Further, the heat-generating film of the present embodiment is not easily affected by the disconnection of the conductive portion, and has high durability and reliability. Therefore, the heat-generating film 10 of the present embodiment can be used as a heat-generating film that can efficiently heat the windows, mirrors, and the like of the vehicle without deteriorating the visibility of the driver of the vehicle and the design of the vehicle.
［発熱フィルムの製造方法］
図４のフローチャートに示すように、発熱フィルム１０の製造方法は、表面１１ｓに、格子溝１１ｃ（第１溝１１Ａ及び第２溝１１Ｂ）が形成された透明フィルム１１を用意することと（図４のステップＳ１）と、格子溝１１ｃに導電性材料を充填して、導電部１３（第１導電部１３Ａ及び第２導電部１３Ｂ）を形成することとを含む（図４のステップＳ２）。発熱フィルム１０は、例えば、導電部１３に対応する凹凸パターンを有するモールドを使用し、インプリントにより凹凸付き透明フィルム１１を形成し、次いで、無電解メッキにより凹部に導電部材を充填することにより製造してもよい。以下に、発熱フィルム１０の製造方法の具体例を図５及び６を参照しながら説明する。 [Manufacturing method of heat-generating film]
As shown in the flowchart of FIG. 4, the method for manufacturing the heat-generatingfilm 10 is to prepare a transparent film 11 having lattice grooves 11c (first groove 11A and second groove 11B) formed on the surface 11s (FIG. 4). Step S1) and filling the lattice groove 11c with a conductive material to form the conductive portion 13 (first conductive portion 13A and second conductive portion 13B) (step S2 in FIG. 4). The heat-generating film 10 is manufactured, for example, by using a mold having a concavo-convex pattern corresponding to the conductive portion 13, forming a concavo-convex transparent film 11 by imprinting, and then filling the recesses with a conductive member by electroless plating. You may. Hereinafter, specific examples of the method for producing the heat-generating film 10 will be described with reference to FIGS. 5 and 6.
図４のフローチャートに示すように、発熱フィルム１０の製造方法は、表面１１ｓに、格子溝１１ｃ（第１溝１１Ａ及び第２溝１１Ｂ）が形成された透明フィルム１１を用意することと（図４のステップＳ１）と、格子溝１１ｃに導電性材料を充填して、導電部１３（第１導電部１３Ａ及び第２導電部１３Ｂ）を形成することとを含む（図４のステップＳ２）。発熱フィルム１０は、例えば、導電部１３に対応する凹凸パターンを有するモールドを使用し、インプリントにより凹凸付き透明フィルム１１を形成し、次いで、無電解メッキにより凹部に導電部材を充填することにより製造してもよい。以下に、発熱フィルム１０の製造方法の具体例を図５及び６を参照しながら説明する。 [Manufacturing method of heat-generating film]
As shown in the flowchart of FIG. 4, the method for manufacturing the heat-generating
＜モールドの準備工程＞
図５（ａ）に示すように、表面に、断面形状として矩形の凸部２０ａが所定間隔で形成された凹凸パターン付きモールド２０を準備する。モールドの凹凸パターンは平面視で複数の直線部が所定間隔で交差する格子パターンである（図２のパターンＡ参照）。凸部２０ａの高さ及び幅並びに凸部２０ａ間の間隔は、前述の導電部１３の設計寸法と同一となるようにする。モールド２０は、例えば、シリコン基板上に塗布したフォトレジストに所定パターンのマスクを介して感光及びエッチングするフォトリソグラフィ法を用いて作製することができる。モールド２０の表面には次の工程のために離型剤を塗布するのが好ましい。 <Mold preparation process>
As shown in FIG. 5A, amold 20 having a concavo-convex pattern in which rectangular convex portions 20a having a rectangular cross-sectional shape are formed at predetermined intervals is prepared on the surface. The uneven pattern of the mold is a lattice pattern in which a plurality of straight lines intersect at predetermined intervals in a plan view (see pattern A in FIG. 2). The height and width of the convex portion 20a and the distance between the convex portions 20a are set to be the same as the design dimensions of the conductive portion 13 described above. The mold 20 can be produced, for example, by using a photolithography method in which a photoresist applied on a silicon substrate is photosensitiveed and etched through a mask having a predetermined pattern. It is preferable to apply a mold release agent to the surface of the mold 20 for the next step.
図５（ａ）に示すように、表面に、断面形状として矩形の凸部２０ａが所定間隔で形成された凹凸パターン付きモールド２０を準備する。モールドの凹凸パターンは平面視で複数の直線部が所定間隔で交差する格子パターンである（図２のパターンＡ参照）。凸部２０ａの高さ及び幅並びに凸部２０ａ間の間隔は、前述の導電部１３の設計寸法と同一となるようにする。モールド２０は、例えば、シリコン基板上に塗布したフォトレジストに所定パターンのマスクを介して感光及びエッチングするフォトリソグラフィ法を用いて作製することができる。モールド２０の表面には次の工程のために離型剤を塗布するのが好ましい。 <Mold preparation process>
As shown in FIG. 5A, a
＜インプリントによる透明フィルムの調製工程＞
次いで、モールド２０の凸部２０ａが形成された表面に、紫外線硬化樹脂のような光硬化性の樹脂を塗布して塗布層２２を形成する。次いで、塗布層２２上に、例えば、ＰＥＴフィルムのような合成樹脂から成る透明支持基材３３を配置して図５（ｂ）に示すような積層体を形成する。次いで、この積層体に、透明支持基材３３側から紫外線の光を照射する。これにより、塗布層２２を構成する光硬化性樹脂を硬化させ、透明樹脂層１２を形成する。次いで、図５（ｃ）に示すように、モールド２０を積層体の透明樹脂層１２から剥離して、モールドの凸部２０ａのパターンに対応する格子状の凹部（格子溝）１１ｃが表面に形成された透明樹脂層１２を備える透明フィルム１１が得られる。 <Preparation process of transparent film by imprint>
Next, a photocurable resin such as an ultraviolet curable resin is applied to the surface of themold 20 on which the convex portion 20a is formed to form the coating layer 22. Next, a transparent support base material 33 made of a synthetic resin such as a PET film is arranged on the coating layer 22 to form a laminate as shown in FIG. 5 (b). Next, the laminated body is irradiated with ultraviolet light from the transparent support base material 33 side. As a result, the photocurable resin constituting the coating layer 22 is cured to form the transparent resin layer 12. Next, as shown in FIG. 5C, the mold 20 is peeled off from the transparent resin layer 12 of the laminated body, and a grid-like concave portion (lattice groove) 11c corresponding to the pattern of the convex portion 20a of the mold is formed on the surface. A transparent film 11 including the transparent resin layer 12 is obtained.
次いで、モールド２０の凸部２０ａが形成された表面に、紫外線硬化樹脂のような光硬化性の樹脂を塗布して塗布層２２を形成する。次いで、塗布層２２上に、例えば、ＰＥＴフィルムのような合成樹脂から成る透明支持基材３３を配置して図５（ｂ）に示すような積層体を形成する。次いで、この積層体に、透明支持基材３３側から紫外線の光を照射する。これにより、塗布層２２を構成する光硬化性樹脂を硬化させ、透明樹脂層１２を形成する。次いで、図５（ｃ）に示すように、モールド２０を積層体の透明樹脂層１２から剥離して、モールドの凸部２０ａのパターンに対応する格子状の凹部（格子溝）１１ｃが表面に形成された透明樹脂層１２を備える透明フィルム１１が得られる。 <Preparation process of transparent film by imprint>
Next, a photocurable resin such as an ultraviolet curable resin is applied to the surface of the
＜無電解メッキによる導電部の形成＞
上記のようにして得られた透明フィルム１１の透明樹脂層１２の凹部１１ｃに以下のようにして無電解メッキにより導電部１３を形成した。 <Formation of conductive parts by electroless plating>
Theconductive portion 13 was formed in the recess 11c of the transparent resin layer 12 of the transparent film 11 obtained as described above by electroless plating as follows.
上記のようにして得られた透明フィルム１１の透明樹脂層１２の凹部１１ｃに以下のようにして無電解メッキにより導電部１３を形成した。 <Formation of conductive parts by electroless plating>
The
（Ａ）メッキ触媒下地層の形成（シランカップリング処理）
無電解メッキを施す際に、メッキ膜の強固な密着性を確保するためにメッキ膜を施す部位にシランカップリング処理を施すことが好ましい。このような処理に用いるシランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシランや、Ｎ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン、３－（Ｎ－フェニル）アミノプロピルトリメトキシシラン等のアミノシラン化合物やその他の反応性官能基を有するシラン化合物を用いることができる。このようなシランカップリング剤の溶液を透明フィルム１１の表面１１ｓの塗布することで、図６（ａ）に示すように、透明樹脂層１２の凹部１１ｃ含む表面に下地層２８を形成する。下地層２８の透明樹脂層１２の表面への密着性を向上させるために、下地層形成材料の溶液の塗布後、透明フィルム１１を加熱してもよい。また、下地層形成材料の溶液の塗布前に、透明樹脂層１２の表面にＵＶ光を照射して透明樹脂層１２の表面の表面改質を行ってもよい。 (A) Formation of plating catalyst base layer (silane coupling treatment)
When performing electroless plating, it is preferable to perform a silane coupling treatment on the portion to be plated in order to ensure strong adhesion of the plating film. Examples of the silane coupling agent used for such treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, and 3-(. Aminosilane compounds such as N-phenyl) aminopropyltrimethoxysilane and other silane compounds having a reactive functional group can be used. By applying such a solution of the silane coupling agent on thesurface 11s of the transparent film 11, as shown in FIG. 6A, the base layer 28 is formed on the surface of the transparent resin layer 12 including the recess 11c. In order to improve the adhesion of the base layer 28 to the surface of the transparent resin layer 12, the transparent film 11 may be heated after applying the solution of the base layer forming material. Further, before applying the solution of the base layer forming material, the surface of the transparent resin layer 12 may be irradiated with UV light to modify the surface of the transparent resin layer 12.
無電解メッキを施す際に、メッキ膜の強固な密着性を確保するためにメッキ膜を施す部位にシランカップリング処理を施すことが好ましい。このような処理に用いるシランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシランや、Ｎ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン、３－（Ｎ－フェニル）アミノプロピルトリメトキシシラン等のアミノシラン化合物やその他の反応性官能基を有するシラン化合物を用いることができる。このようなシランカップリング剤の溶液を透明フィルム１１の表面１１ｓの塗布することで、図６（ａ）に示すように、透明樹脂層１２の凹部１１ｃ含む表面に下地層２８を形成する。下地層２８の透明樹脂層１２の表面への密着性を向上させるために、下地層形成材料の溶液の塗布後、透明フィルム１１を加熱してもよい。また、下地層形成材料の溶液の塗布前に、透明樹脂層１２の表面にＵＶ光を照射して透明樹脂層１２の表面の表面改質を行ってもよい。 (A) Formation of plating catalyst base layer (silane coupling treatment)
When performing electroless plating, it is preferable to perform a silane coupling treatment on the portion to be plated in order to ensure strong adhesion of the plating film. Examples of the silane coupling agent used for such treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, and 3-(. Aminosilane compounds such as N-phenyl) aminopropyltrimethoxysilane and other silane compounds having a reactive functional group can be used. By applying such a solution of the silane coupling agent on the
次いで、下地層２８が凹部１１ｃの内表面にだけ存在するような処理を施す。この処理は、例えば、凹部１１ｃの開口部を除く透明樹脂層１２の表面上の下地層２８にだけＵＶ光を照射することを含む。必要に応じて、光を遮断するマスク等を用いてもよい。この結果、図６（ｂ）に示すように凹部１１ｃの内表面にだけ下地層２８が存在する透明フィルム１１を得ることができる。
Next, a treatment is performed so that the base layer 28 exists only on the inner surface of the recess 11c. This treatment includes, for example, irradiating only the base layer 28 on the surface of the transparent resin layer 12 excluding the opening of the recess 11c with UV light. If necessary, a mask or the like that blocks light may be used. As a result, as shown in FIG. 6B, the transparent film 11 in which the base layer 28 exists only on the inner surface of the recess 11c can be obtained.
（Ｂ）メッキ触媒の担持
次に、公知のメッキ触媒液に、上記のようにして得られた凹部１１ｃの内表面にだけ下地層２８が存在する透明フィルム１１を浸漬する。これにより、凹部１１ｃの内部にのみメッキ触媒である金属のイオン（例えば、パラジウムイオン）が担持された透明フィルム（メッキ用透明フィルムの前駆体）を得る。メッキ触媒液として、塩化パラジウム（ＩＩ）溶液やテトラクロリド金（ＩＩＩ）酸溶液を使用することができる。さらに、この透明フィルムを還元処理することで、凹部１１ｃの内表面にだけパラジウムのようなメッキ触媒が付着した透明フィルム（メッキ用透明フィルム）を得ることができる。 (B) Supporting the Plating Catalyst Next, thetransparent film 11 in which the base layer 28 exists only on the inner surface of the recess 11c obtained as described above is immersed in a known plating catalyst solution. As a result, a transparent film (a precursor of a transparent film for plating) in which metal ions (for example, palladium ions) as a plating catalyst are supported only inside the recess 11c is obtained. As the plating catalyst solution, a palladium (II) chloride solution or a gold (III) tetrachloride solution can be used. Further, by reducing the transparent film, a transparent film (transparent film for plating) in which a plating catalyst such as palladium is attached only to the inner surface of the recess 11c can be obtained.
次に、公知のメッキ触媒液に、上記のようにして得られた凹部１１ｃの内表面にだけ下地層２８が存在する透明フィルム１１を浸漬する。これにより、凹部１１ｃの内部にのみメッキ触媒である金属のイオン（例えば、パラジウムイオン）が担持された透明フィルム（メッキ用透明フィルムの前駆体）を得る。メッキ触媒液として、塩化パラジウム（ＩＩ）溶液やテトラクロリド金（ＩＩＩ）酸溶液を使用することができる。さらに、この透明フィルムを還元処理することで、凹部１１ｃの内表面にだけパラジウムのようなメッキ触媒が付着した透明フィルム（メッキ用透明フィルム）を得ることができる。 (B) Supporting the Plating Catalyst Next, the
（Ｃ）無電解メッキ
最後に、透明フィルム１１（メッキ用透明フィルム）を無電解メッキ液に浸漬して無電解メッキを施す。無電解メッキにより、凹部１１ｃの内部にのみ導電性材料が形成される。こうして、図６（ｃ）に示すような凹部１１ｃの内部に導電部１３が形成された発熱フィルム１０を得ることができる。 (C) Electroless plating Finally, the transparent film 11 (transparent film for plating) is immersed in an electroless plating solution to perform electroless plating. By electroless plating, a conductive material is formed only inside therecess 11c. In this way, it is possible to obtain the heat-generating film 10 in which the conductive portion 13 is formed inside the recess 11c as shown in FIG. 6 (c).
最後に、透明フィルム１１（メッキ用透明フィルム）を無電解メッキ液に浸漬して無電解メッキを施す。無電解メッキにより、凹部１１ｃの内部にのみ導電性材料が形成される。こうして、図６（ｃ）に示すような凹部１１ｃの内部に導電部１３が形成された発熱フィルム１０を得ることができる。 (C) Electroless plating Finally, the transparent film 11 (transparent film for plating) is immersed in an electroless plating solution to perform electroless plating. By electroless plating, a conductive material is formed only inside the
＜変形例＞
上述の実施形態では、導電部１３が形成する格子パターン（格子状のパターン）として、図２に示す、パターンＡを用いたが本実施形態はこれに限定されない。平面視で複数の直線部（導電部１３）が所定間隔で交差するパターンであれば、格子パターンとして用いることができる。例えば、パターンＡでは、第１間隔Ｐ１より第２間隔Ｐ２が長いため、各格子の平面形状は矩形（長方形）であるが、第１間隔Ｐ１と、第２間隔Ｐ２とは等しくてもよい。この場合、各格子の平面形状は正方形となる。 <Modification example>
In the above-described embodiment, the pattern A shown in FIG. 2 is used as the lattice pattern (lattice-like pattern) formed by theconductive portion 13, but the present embodiment is not limited to this. A pattern in which a plurality of straight lines (conductive parts 13) intersect at predetermined intervals in a plan view can be used as a lattice pattern. For example, in the pattern A, since the second interval P2 is longer than the first interval P1, the planar shape of each lattice is rectangular, but the first interval P1 and the second interval P2 may be equal. In this case, the planar shape of each grid is square.
上述の実施形態では、導電部１３が形成する格子パターン（格子状のパターン）として、図２に示す、パターンＡを用いたが本実施形態はこれに限定されない。平面視で複数の直線部（導電部１３）が所定間隔で交差するパターンであれば、格子パターンとして用いることができる。例えば、パターンＡでは、第１間隔Ｐ１より第２間隔Ｐ２が長いため、各格子の平面形状は矩形（長方形）であるが、第１間隔Ｐ１と、第２間隔Ｐ２とは等しくてもよい。この場合、各格子の平面形状は正方形となる。 <Modification example>
In the above-described embodiment, the pattern A shown in FIG. 2 is used as the lattice pattern (lattice-like pattern) formed by the
また、図２に示すパターンＡでは、第１導電部１３Ａは等間隔の第１間隔Ｐ１で配置されるが、本実施形態の格子パターンはこれに限定されない。本実施形態の格子パターンは、図７（ａ）に示すパターンＤ１のように、複数の第１導電部１３Ａにより第１複線部１３ＡＷが構成されてもよい。隣り合う２つの第１複線部１３ＡＷは第１間隔Ｐ１で配置されている。第１複線部１３ＡＷにおいて、複数の第１導電部１３Ａは、第１間隔Ｐ１より狭い第４間隔Ｐ４で配置される。第１導電部１３Ａが第１複線部１３ＡＷを構成することにより、交点Ｒの数が増加し、断線影響面積が小さくなる。これにより、パターンＤ１を用いた発熱フィルム１０は導電部１３の断線の影響をより受け難くなり、耐久性及び信頼性がより高くなる。第４間隔Ｐ４は、例えば、０．２～２０μｍ、０．３～１５μｍ又は０．５～１０μｍであってよい。パターンＤ１では、第１複線部１３ＡＷは３個（３本）の第１導電部１３Ａにより構成されるが、本変形例はこれに限定されない。第１複線部１３ＡＷを構成する第１導電部１３Ａの数は、例えば、２～１０個、２～５個、又は２～３個としてよい。尚、第４間隔Ｐ４は、第１方向に垂直な方向における距離であり、第１複線部１３ＡＷにおける、隣り合う２つの第１導電部１３Ａの対向する縁（端部）の間の距離である。
Further, in the pattern A shown in FIG. 2, the first conductive portions 13A are arranged at the first interval P1 at equal intervals, but the lattice pattern of the present embodiment is not limited to this. In the lattice pattern of the present embodiment, as in the pattern D1 shown in FIG. 7A, the first double-track portion 13AW may be formed by the plurality of first conductive portions 13A. The two adjacent first double-track portions 13AW are arranged at the first interval P1. In the first double track portion 13AW, the plurality of first conductive portions 13A are arranged at a fourth interval P4 narrower than the first interval P1. By forming the first double-track portion 13AW by the first conductive portion 13A, the number of intersections R increases and the area affected by disconnection decreases. As a result, the heat-generating film 10 using the pattern D1 is less susceptible to the influence of the disconnection of the conductive portion 13, and the durability and reliability are further improved. The fourth interval P4 may be, for example, 0.2 to 20 μm, 0.3 to 15 μm, or 0.5 to 10 μm. In the pattern D1, the first double-track portion 13AW is composed of three (three) first conductive portions 13A, but this modification is not limited to this. The number of the first conductive portions 13A constituting the first double-track portion 13AW may be, for example, 2 to 10, 2 to 5, or 2 to 3. The fourth interval P4 is a distance in a direction perpendicular to the first direction, and is a distance between opposite edges (ends) of two adjacent first conductive portions 13A in the first double-track portion 13AW. ..
本実施形態の格子パターンは、図７（ｂ）に示すパターンＤ２のように、複数の第２導電部１３Ｂにより第２複線部１３ＢＷが構成されてもよい。隣り合う２つの第２複線部１３ＢＷは、第１方向において第２間隔Ｐ２で配置されている。第２複線部１３ＢＷにおいて、複数の第２導電部１３Ｂは、第１方向において第２間隔Ｐ２より狭い第５間隔Ｐ５で配置される。第２導電部１３Ｂが第２複線部１３ＢＷを構成することにより、交点Ｒの数が増加し、断線影響面積が小さくなる。これにより、パターンＤ２を用いた発熱フィルム１０は導電部１３の断線の影響をより受け難くなり、耐久性及び信頼性がより高くなる。第５間隔Ｐ５は、例えば、０．５～２０μｍ、０．７～１５μｍ又は１．０～１０μｍであってよい。パターンＤ２では、第２複線部１３ＢＷは３個（３本）の第２導電部１３Ｂにより構成されるが、本変形例はこれに限定されない。第２複線部１３ＢＷを構成する第２導電部１３Ｂの数は、例えば、２～１０個、２～５個、又は２～３個としてよい。尚、第５間隔Ｐ５は、第１方向における距離であり、第２複線部１３ＢＷにおける、隣り合う２つの第２導電部１３Ｂの対向する縁（端部）の間の距離である。
In the lattice pattern of the present embodiment, as in the pattern D2 shown in FIG. 7B, the second double-track portion 13BW may be formed by the plurality of second conductive portions 13B. The two adjacent second double-track portions 13BW are arranged at a second interval P2 in the first direction. In the second double-track portion 13BW, the plurality of second conductive portions 13B are arranged at a fifth interval P5 narrower than the second interval P2 in the first direction. By forming the second double-track portion 13BW by the second conductive portion 13B, the number of intersections R increases and the area affected by disconnection decreases. As a result, the heat-generating film 10 using the pattern D2 is less susceptible to the influence of the disconnection of the conductive portion 13, and the durability and reliability are further improved. The fifth interval P5 may be, for example, 0.5 to 20 μm, 0.7 to 15 μm, or 1.0 to 10 μm. In the pattern D2, the second double-track portion 13BW is composed of three (three) second conductive portions 13B, but this modification is not limited to this. The number of the second conductive portions 13B constituting the second double-track portion 13BW may be, for example, 2 to 10, 2 to 5, or 2 to 3. The fifth interval P5 is a distance in the first direction, and is a distance between opposite edges (ends) of two adjacent second conductive portions 13B in the second double-track portion 13BW.
パターンＤ１（図７（ａ））又はパターンＤ２（図７（ｂ））を用いた発熱フィルム１０では、上述のように導電部１３の断線の影響を受け難いため、導電部１３の線幅Ｗを小さく（狭く）してもよい。導電部１３の線幅Ｗを小さくすることで、発熱フィルム１０の透明性（透過率）がより向上し、導電部１３の骨見えもより抑制できる。また、導電部１３の線幅Ｗが小さい場合でも、第１複線部１３ＡＷ及び第２複線部１３ＢＷは複数の導電部１３（第１導電部１３Ａ、第２導電部１３Ｂ）によって構成されるため、発熱フィルム１０は十分な発熱量を得られる。パターンＤ１及びパターンＤ２において、導電部１３の線幅Ｗは、例えば、０．２～１０μｍ、好ましくは０．３～５μｍ、又は０．５～３μｍとしてよい。
Since the heat-generating film 10 using the pattern D1 (FIG. 7 (a)) or the pattern D2 (FIG. 7 (b)) is not easily affected by the disconnection of the conductive portion 13 as described above, the line width W of the conductive portion 13 May be made smaller (narrower). By reducing the line width W of the conductive portion 13, the transparency (transmittance) of the heat generating film 10 can be further improved, and the bone appearance of the conductive portion 13 can be further suppressed. Further, even when the line width W of the conductive portion 13 is small, the first double-track portion 13AW and the second double-track portion 13BW are composed of a plurality of conductive portions 13 (first conductive portion 13A, second conductive portion 13B). The heat-generating film 10 can obtain a sufficient amount of heat generation. In the pattern D1 and the pattern D2, the line width W of the conductive portion 13 may be, for example, 0.2 to 10 μm, preferably 0.3 to 5 μm, or 0.5 to 3 μm.
本実施形態の格子パターンは、図８に示すパターンＥのように、第１方向と第２方向とか直交しなくてもよい。この場合、パターンＥにおける格子の形状は平行四辺形となる。パターンＥでは、第２導電部１３Ｂの延在方向である第２方向を第１方向に近づける（傾ける）ことで、引張などの応力がかかった際に導電配線が交わる交差点部へかかる局所的な応力を緩和することができる。
The lattice pattern of the present embodiment does not have to be orthogonal to the first direction and the second direction as in the pattern E shown in FIG. In this case, the shape of the grid in pattern E is a parallelogram. In the pattern E, by bringing (tilting) the second direction, which is the extending direction of the second conductive portion 13B, to the first direction, a local portion applied to the intersection where the conductive wiring intersects when stress such as tension is applied. The stress can be relieved.
以上、本発明を実施形態により説明してきたが、本発明の発熱フィルム及びこれの製造方法は上記実施形態に限定されず、特許請求の範囲に記載した技術的思想の範囲内で適宜改変することができる。
Although the present invention has been described above by embodiment, the heat-generating film of the present invention and the method for producing the same are not limited to the above-described embodiment, and may be appropriately modified within the scope of the technical idea described in the claims. Can be done.
以下に、発熱フィルム及びその製造方法の実施例を説明するが、本発明はそれらに限定されない。
Examples of the heat-generating film and the method for producing the heat-generating film will be described below, but the present invention is not limited thereto.
［実施例１］
＜透明フィルムの調製工程＞
モールド２０として、一方の表面に断面形状が矩形（高さ２μｍ、幅１μｍ）の線状の凸部により、図２に示す格子パターン（パターンＡ）が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を準備した（図５（ａ）参照）。Ｓｉウエハ表面において、第２方向における、隣り合う凸部間の間隔（第１間隔Ｐ１に相当）は１００μｍとし、第１方向における、隣り合う凸部の間隔（第２間隔Ｐ２に相当）は５０００μｍとした。尚、凸部間の間隔とは、第１方向又は第２方向における、隣り合う２つの凸部の対向する縁（端部）の間の距離である。凸部を有する表面に、フッ素系精密離型剤の膜（膜厚約３０ｎｍの超薄膜）を形成することにより離型処理を施した。 [Example 1]
<Transparent film preparation process>
As themold 20, a Si wafer (300 mm × 300 mm) in which a lattice pattern (pattern A) shown in FIG. 2 is formed by linear convex portions having a rectangular cross-sectional shape (height 2 μm, width 1 μm) on one surface. Was prepared (see FIG. 5 (a)). On the Si wafer surface, the distance between adjacent convex portions in the second direction (corresponding to the first distance P1) is 100 μm, and the distance between adjacent convex parts in the first direction (corresponding to the second distance P2) is 5000 μm. And said. The distance between the convex portions is the distance between the opposite edges (ends) of the two adjacent convex portions in the first direction or the second direction. A mold release treatment was performed by forming a film of a fluorine-based precision mold release agent (an ultrathin film having a film thickness of about 30 nm) on the surface having a convex portion.
＜透明フィルムの調製工程＞
モールド２０として、一方の表面に断面形状が矩形（高さ２μｍ、幅１μｍ）の線状の凸部により、図２に示す格子パターン（パターンＡ）が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を準備した（図５（ａ）参照）。Ｓｉウエハ表面において、第２方向における、隣り合う凸部間の間隔（第１間隔Ｐ１に相当）は１００μｍとし、第１方向における、隣り合う凸部の間隔（第２間隔Ｐ２に相当）は５０００μｍとした。尚、凸部間の間隔とは、第１方向又は第２方向における、隣り合う２つの凸部の対向する縁（端部）の間の距離である。凸部を有する表面に、フッ素系精密離型剤の膜（膜厚約３０ｎｍの超薄膜）を形成することにより離型処理を施した。 [Example 1]
<Transparent film preparation process>
As the
離型処理を施したモールド２０表面に、アクリル系ＵＶ硬化樹脂（以下、場合により単に「ＵＶ硬化樹脂」と称する）をドロップキャストして、ＵＶ硬化樹脂からなる塗布層２２を厚さ１３μｍで形成した。次いで、この塗布層２２上に厚さ１００μｍのＰＥＴフィルム（透明支持基材３３）を配置して、ＵＶ硬化樹脂からなる塗布層２２（未硬化の透明樹脂層１２）をモールド２０とＰＥＴフィルム３３とで挟み込んだ積層体とした（図５（ｂ）参照）。次いで、この積層体に、ＰＥＴフィルム３３側から高圧水銀ランプを用いて中心波長３６５ｎｍのＵＶ光を２０００ｍＪ／ｃｍ２にて照射し、塗布層２２を形成するＵＶ硬化樹脂を硬化させ、透明樹脂層１２（厚さ１０μｍ）を形成した。次いで、モールド２０を積層体の透明樹脂層２２から剥離して、モールド２０の凸部のパターン形状に由来した格子状の凹部が表面に形成された透明樹脂層２２を備える透明フィルム１１を得た（図５（ｃ）参照）。透明フィルム１１の表面において、第２方向における、隣り合う凹部間の間隔（第１間隔Ｐ１に相当）は１００μｍであり、第１方向における、隣り合う凹部の間隔（第２間隔Ｐ２に相当）は５０００μｍであった。
An acrylic UV curable resin (hereinafter, sometimes simply referred to as "UV curable resin") is drop cast on the surface of the mold 20 that has been subjected to the mold release treatment to form a coating layer 22 made of the UV curable resin having a thickness of 13 μm. did. Next, a PET film (transparent support base material 33) having a thickness of 100 μm is placed on the coating layer 22, and the coating layer 22 (uncured transparent resin layer 12) made of UV curable resin is molded into the mold 20 and the PET film 33. It was made into a laminated body sandwiched between and (see FIG. 5 (b)). Next, the laminate was irradiated with UV light having a center wavelength of 365 nm from the PET film 33 side using a high-pressure mercury lamp at 2000 mJ / cm 2 , and the UV curable resin forming the coating layer 22 was cured to cure the transparent resin layer. 12 (thickness 10 μm) was formed. Next, the mold 20 was peeled off from the transparent resin layer 22 of the laminated body to obtain a transparent film 11 provided with the transparent resin layer 22 in which lattice-shaped concave portions derived from the pattern shape of the convex portion of the mold 20 were formed on the surface. (See FIG. 5 (c)). On the surface of the transparent film 11, the distance between adjacent recesses in the second direction (corresponding to the first gap P1) is 100 μm, and the distance between the adjacent recesses in the first direction (corresponding to the second gap P2) is 100 μm. It was 5000 μm.
＜メッキ触媒下地層を形成する工程＞
シランカップリン処理に用いる下地層原料溶液を次のようにして調製した。エタノール２００ｍＬ中に３－アミノプロピルトリエトキシシラン１ｍＬを添加し、３０分間撹拌し、３－アミノプロピルトリエトキシシランの溶液（下地層原料溶液）（溶媒：エタノール、３－アミノプロピルトリエトキシシランの濃度：０．５体積％）とした。 <Step of forming the plating catalyst base layer>
The base layer raw material solution used for the silane coupling treatment was prepared as follows. 1 mL of 3-aminopropyltriethoxysilane is added to 200 mL of ethanol, and the mixture is stirred for 30 minutes to prepare a solution of 3-aminopropyltriethoxysilane (base layer raw material solution) (solvent: ethanol, concentration of 3-aminopropyltriethoxysilane). : 0.5% by volume).
シランカップリン処理に用いる下地層原料溶液を次のようにして調製した。エタノール２００ｍＬ中に３－アミノプロピルトリエトキシシラン１ｍＬを添加し、３０分間撹拌し、３－アミノプロピルトリエトキシシランの溶液（下地層原料溶液）（溶媒：エタノール、３－アミノプロピルトリエトキシシランの濃度：０．５体積％）とした。 <Step of forming the plating catalyst base layer>
The base layer raw material solution used for the silane coupling treatment was prepared as follows. 1 mL of 3-aminopropyltriethoxysilane is added to 200 mL of ethanol, and the mixture is stirred for 30 minutes to prepare a solution of 3-aminopropyltriethoxysilane (base layer raw material solution) (solvent: ethanol, concentration of 3-aminopropyltriethoxysilane). : 0.5% by volume).
上述のようにして得られた透明フィルム１１の透明樹脂層１２側表面の全面に３０００ｍＪ／ｃｍ２にてＵＶ光を照射して、予め透明樹脂層１２の表面の表面改質を行った。次いで、バーコーターを用いて、下地層原料溶液を前記表面改質後の透明フィルム１１の透明樹脂層１２側の表面に膜厚（Ｗｅｔ膜厚）が１０μｍとなるように塗布した。透明樹脂層１２側の表面の全面（凹部１１ｃの内表面を含む全面）に、３－アミノプロピルトリエトキシシランからなる下地層（下地層の材料である３－アミノプロピルトリエトキシシランと透明フィルム上の水酸基との反応物からなる層）２８を形成した。その後、透明フィルム１１の透明樹脂層１２側の表面及び凹部１１ｃの内表面に３－アミノプロピルトリエトキシシランからなる層（下地層２８）がより十分に密着するように、透明フィルム１１を７０℃に加熱されたオーブン内で３分間加熱処理を施した。このようにして、透明フィルム１１の透明樹脂層１２側の表面及び凹部１１ｃの内表面の全面に亘って、３－アミノプロピルトリエトキシシランからなる下地層２８が形成された透明フィルム１１を得た（図６（ａ）参照）。
The entire surface of the transparent resin layer 12 side surface of the transparent film 11 obtained as described above was irradiated with UV light at 3000 mJ / cm 2 , and the surface of the transparent resin layer 12 was modified in advance. Next, using a bar coater, the base layer raw material solution was applied to the surface of the transparent film 11 after the surface modification on the transparent resin layer 12 side so that the film thickness (Wet film thickness) was 10 μm. On the entire surface of the transparent resin layer 12 side (the entire surface including the inner surface of the recess 11c), an underlayer made of 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane, which is a material of the underlayer, and a transparent film). A layer (28) composed of a reaction product with the hydroxyl group of the above was formed. After that, the transparent film 11 is heated at 70 ° C. so that the layer (underlayer 28) made of 3-aminopropyltriethoxysilane is more sufficiently adhered to the surface of the transparent film 11 on the transparent resin layer 12 side and the inner surface of the recess 11c. The film was heat-treated for 3 minutes in a heated oven. In this way, a transparent film 11 having a base layer 28 made of 3-aminopropyltriethoxysilane formed over the entire surface of the transparent film 11 on the transparent resin layer 12 side and the inner surface of the recess 11c was obtained. (See FIG. 6 (a)).
次いで、下地層２８が形成された透明フィルム１１の下地層２８側表面の全面にＵＶ光を照射した。これにより、透明フィルム１１表面および凹部１１ｃの内表面のうち、透明フィルム１１表面近傍に存在する下地層２８を除去した。この際、凹部１１ｃの内表面のうち、透明フィルム１１表面近傍を除く内表面には下地層が存在している。すなわち、透明フィルム１１の凹部１１ｃの内表面にのみ選択的に下地層２８が形成された透明フィルム１１を得た（図６（ｂ）参照）。
Next, the entire surface of the transparent film 11 on which the base layer 28 was formed on the base layer 28 side was irradiated with UV light. As a result, of the surface of the transparent film 11 and the inner surface of the recess 11c, the base layer 28 existing near the surface of the transparent film 11 was removed. At this time, of the inner surface of the recess 11c, the base layer exists on the inner surface except the vicinity of the surface of the transparent film 11. That is, a transparent film 11 in which the base layer 28 was selectively formed only on the inner surface of the recess 11c of the transparent film 11 was obtained (see FIG. 6B).
＜凹部の内部への触媒選択担持工程＞
メッキ触媒液として、０．２ｇの塩化パラジウム（ＩＩ）に塩酸１．０ｍＬを加え、加熱して溶解させた後、イオン交換水１Ｌを加えることにより、塩化パラジウム（ＩＩ）の溶液を得た。次いで、得られたメッキ触媒液に、上述のようにして得られた凹部１１ｃの内表面にのみ下地層２８が形成された透明フィルム１１を室温条件下で１０分間浸漬させることで、凹部１１ｃの内表面上に形成された下地層２８上にのみパラジウムイオンが担持されたメッキ用透明フィルムの前駆体が得られた。 <Catalyst selective loading process inside the recess>
As a plating catalyst solution, 1.0 mL of hydrochloric acid was added to 0.2 g of palladium (II) chloride, heated to dissolve it, and then 1 L of ion-exchanged water was added to obtain a solution of palladium (II) chloride. Next, thetransparent film 11 having the base layer 28 formed only on the inner surface of the recess 11c obtained as described above is immersed in the obtained plating catalyst solution for 10 minutes under room temperature conditions to form the recess 11c. A precursor of a transparent film for plating in which palladium ions were supported only on the base layer 28 formed on the inner surface was obtained.
メッキ触媒液として、０．２ｇの塩化パラジウム（ＩＩ）に塩酸１．０ｍＬを加え、加熱して溶解させた後、イオン交換水１Ｌを加えることにより、塩化パラジウム（ＩＩ）の溶液を得た。次いで、得られたメッキ触媒液に、上述のようにして得られた凹部１１ｃの内表面にのみ下地層２８が形成された透明フィルム１１を室温条件下で１０分間浸漬させることで、凹部１１ｃの内表面上に形成された下地層２８上にのみパラジウムイオンが担持されたメッキ用透明フィルムの前駆体が得られた。 <Catalyst selective loading process inside the recess>
As a plating catalyst solution, 1.0 mL of hydrochloric acid was added to 0.2 g of palladium (II) chloride, heated to dissolve it, and then 1 L of ion-exchanged water was added to obtain a solution of palladium (II) chloride. Next, the
このメッキ用透明フィルムの前駆体を、イオン交換水で水洗した後、イオン交換水１Ｌに対して、ジメチルアミンボランを３．２ｇ溶解した還元用の溶液（還元剤を含む処理液）に室温条件で１０分間浸漬させた。このようにして、メッキ用透明フィルムの前駆体中の凹部内に選択的に担持されたパラジウムイオンを還元して金属パラジウムとすることにより、凹部の内部に金属パラジウムからなる触媒層が選択的に担持されたメッキ用透明フィルムを得た。
After washing the precursor of this transparent film for plating with water with ion-exchanged water, 3.2 g of dimethylamine borane was dissolved in 1 L of ion-exchanged water in a reducing solution (treatment liquid containing a reducing agent) at room temperature. Was immersed for 10 minutes. In this way, the palladium ion selectively supported in the recess in the precursor of the transparent film for plating is reduced to metallic palladium, so that the catalyst layer made of metallic palladium is selectively formed inside the recess. A supported transparent film for plating was obtained.
＜無電解メッキ工程＞
下記のような組成の無電解メッキ液（無電解銅メッキ液）を調製した。
硫酸銅五水和物（Ｃｕ２＋として）：０．０３ｍｏｌ／Ｌ
ホルムアルデヒド：０．２ｍｏｌ／Ｌ
ＥＤＴＡ：０．２４ｍｏｌ／Ｌ
ポリエチレングリコール： １００ｐｐｍ
２，２’－ビピリジル： １０ｐｐｍ
水酸化ナトリウム：ｐＨが１２．５～１３．２となる添加量
残余：イオン交換水 <Electroless plating process>
An electroless plating solution (electroless copper plating solution) having the following composition was prepared.
Copper sulfate pentahydrate (as Cu 2+ ): 0.03 mol / L
Formaldehyde: 0.2 mol / L
EDTA: 0.24 mol / L
Polyethylene glycol: 100 ppm
2,2'-bipyridyl: 10 ppm
Sodium hydroxide: Addition amount that makes the pH 12.5 to 13.2 Residual: Ion-exchanged water
下記のような組成の無電解メッキ液（無電解銅メッキ液）を調製した。
硫酸銅五水和物（Ｃｕ２＋として）：０．０３ｍｏｌ／Ｌ
ホルムアルデヒド：０．２ｍｏｌ／Ｌ
ＥＤＴＡ：０．２４ｍｏｌ／Ｌ
ポリエチレングリコール： １００ｐｐｍ
２，２’－ビピリジル： １０ｐｐｍ
水酸化ナトリウム：ｐＨが１２．５～１３．２となる添加量
残余：イオン交換水 <Electroless plating process>
An electroless plating solution (electroless copper plating solution) having the following composition was prepared.
Copper sulfate pentahydrate (as Cu 2+ ): 0.03 mol / L
Formaldehyde: 0.2 mol / L
EDTA: 0.24 mol / L
Polyethylene glycol: 100 ppm
2,2'-bipyridyl: 10 ppm
Sodium hydroxide: Addition amount that makes the pH 12.5 to 13.2 Residual: Ion-exchanged water
メッキ用透明フィルム１１をメッキ浴中の無電解メッキ液に、浸漬して、温度：６０℃、時間：１０分の条件で無電解メッキを施した。その後、純水で洗浄し、乾燥した。メッキ用透明フィルム１１の凹部１１ｃの内部にのみ銅のメッキ皮膜が形成されていた。こうして、凹部１１ｃの内部に銅からなる金属導電層（導電部１３）が形成された発熱フィルム１０を得た（図６（ｃ）参照）。尚、導電部の高さＨは透明フィルムの凹部の深さＤと略同一とした。
The transparent film 11 for plating was immersed in an electroless plating solution in a plating bath, and electroless plating was performed under the conditions of temperature: 60 ° C. and time: 10 minutes. Then, it was washed with pure water and dried. A copper plating film was formed only inside the recess 11c of the transparent film 11 for plating. In this way, a heat-generating film 10 in which a metal conductive layer (conductive portion 13) made of copper was formed inside the recess 11c was obtained (see FIG. 6C). The height H of the conductive portion was substantially the same as the depth D of the recess of the transparent film.
［実施例２～１０］
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表１に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Examples 2 to 10]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 1 are formed on the transparent film. Changed.
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表１に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Examples 2 to 10]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 1 are formed on the transparent film. Changed.
［実施例１１］
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更し、更に、無電解メッキ液を変更して無電解ニッケルメッキにより導電部を形成したこと以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表１に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び第２方向における凸部間の間隔、凸部の断面形状（高さ及び幅）を変更した。無電解メッキには、以下の組成の無電解メッキ液（無電解ニッケルメッキ液、ｐＨ範囲：５．０～５．５）を用いて無電解メッキを施した（温度：５０℃、時間：５分）。
硫酸ニッケル六水和物（Ｎｉ２＋として）：０．１０ｍｏｌ／Ｌ
酢酸アンモニウム：０．４０ｍｏｌ／Ｌ
リン酸二水素ナトリウムに水和物：０．２０ｍｏｌ／Ｌ
残余：イオン交換水
[Example 11]
The heat-generating film was formed by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed, and the electroless plating solution was changed to form a conductive portion by electroless nickel plating. Manufactured. The spacing between the convex portions in the first direction and the second direction of the Si wafer and the cross-sectional shape (height and width) of the convex portions were changed so that the patterns of the sizes shown in Table 1 were formed on the transparent film. For electroless plating, electroless plating was performed using an electroless plating solution (electroless nickel plating solution, pH range: 5.0 to 5.5) having the following composition (temperature: 50 ° C., time: 5). Minutes).
Nickel sulfate hexahydrate (as Ni 2+ ): 0.10 mol / L
Ammonium acetate: 0.40 mol / L
Hydrate to sodium dihydrogen phosphate: 0.20 mol / L
Residual: Ion-exchanged water
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更し、更に、無電解メッキ液を変更して無電解ニッケルメッキにより導電部を形成したこと以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表１に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び第２方向における凸部間の間隔、凸部の断面形状（高さ及び幅）を変更した。無電解メッキには、以下の組成の無電解メッキ液（無電解ニッケルメッキ液、ｐＨ範囲：５．０～５．５）を用いて無電解メッキを施した（温度：５０℃、時間：５分）。
硫酸ニッケル六水和物（Ｎｉ２＋として）：０．１０ｍｏｌ／Ｌ
酢酸アンモニウム：０．４０ｍｏｌ／Ｌ
リン酸二水素ナトリウムに水和物：０．２０ｍｏｌ／Ｌ
残余：イオン交換水
[Example 11]
The heat-generating film was formed by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed, and the electroless plating solution was changed to form a conductive portion by electroless nickel plating. Manufactured. The spacing between the convex portions in the first direction and the second direction of the Si wafer and the cross-sectional shape (height and width) of the convex portions were changed so that the patterns of the sizes shown in Table 1 were formed on the transparent film. For electroless plating, electroless plating was performed using an electroless plating solution (electroless nickel plating solution, pH range: 5.0 to 5.5) having the following composition (temperature: 50 ° C., time: 5). Minutes).
Nickel sulfate hexahydrate (as Ni 2+ ): 0.10 mol / L
Ammonium acetate: 0.40 mol / L
Hydrate to sodium dihydrogen phosphate: 0.20 mol / L
Residual: Ion-exchanged water
［実施例１２］
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ａ）に示すパターンＤ１が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ１において、第１複線部１３ＡＷを構成する第１導電部１３Ａの数は３個（３本）とし、第４間隔Ｐ４は１０μｍとした。 [Example 12]
As the mold, the same as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D1, the number of the firstconductive portions 13A constituting the first double-track portion 13AW was set to 3 (3), and the fourth interval P4 was set to 10 μm.
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ａ）に示すパターンＤ１が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ１において、第１複線部１３ＡＷを構成する第１導電部１３Ａの数は３個（３本）とし、第４間隔Ｐ４は１０μｍとした。 [Example 12]
As the mold, the same as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D1, the number of the first
［実施例１３］
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ｂ）に示すパターンＤ２が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ２において、第２複線部１３ＢＷを構成する第２導電部１３Ｂの数は３個（本）とし、第５間隔Ｐ５は１０μｍとした。 [Example 13]
As the mold, a Si wafer (300 mm × 300 mm) in which the pattern D2 shown in FIG. 7 (b) is formed by a linear convex portion having a rectangular cross section on one surface is used, as in the first embodiment. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D2, the number of the secondconductive portions 13B constituting the second double-track portion 13BW was set to 3 (lines), and the fifth interval P5 was set to 10 μm.
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ｂ）に示すパターンＤ２が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ２において、第２複線部１３ＢＷを構成する第２導電部１３Ｂの数は３個（本）とし、第５間隔Ｐ５は１０μｍとした。 [Example 13]
As the mold, a Si wafer (300 mm × 300 mm) in which the pattern D2 shown in FIG. 7 (b) is formed by a linear convex portion having a rectangular cross section on one surface is used, as in the first embodiment. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D2, the number of the second
［実施例１４及び１５］
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により、発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Examples 14 and 15]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Changed.
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により、発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Examples 14 and 15]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Changed.
［実施例１６］
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ａ）に示すパターンＤ１が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ１において、第１複線部１３ＡＷを構成する第１導電部１３Ａの数は１０個（１０本）とし、第４間隔Ｐ４は２μｍとした。 [Example 16]
As the mold, the same as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D1, the number of the firstconductive portions 13A constituting the first double-track portion 13AW was 10 (10), and the fourth interval P4 was 2 μm.
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図７（ａ）に示すパターンＤ１が形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。透明フィルム上に表２に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を調整した。また、パターンＤ１において、第１複線部１３ＡＷを構成する第１導電部１３Ａの数は１０個（１０本）とし、第４間隔Ｐ４は２μｍとした。 [Example 16]
As the mold, the same as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern D1 shown in FIG. 7 (a) is formed by a linear convex portion having a rectangular cross section on one surface is used. A heat-generating film was produced by the same method. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 2 are formed on the transparent film. Was adjusted. Further, in the pattern D1, the number of the first
［比較例１及び２］
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により、発熱フィルムを製造した。透明フィルム上に表３に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Comparative Examples 1 and 2]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 3 are formed on the transparent film. Changed.
モールドとして用いるＳｉウエハ上のパターンＡのサイズを変更した以外は、実施例１と同様の方法により、発熱フィルムを製造した。透明フィルム上に表３に示すサイズのパターンが形成されるように、Ｓｉウエハの第１方向及び／又は第２方向における凸部間の間隔、凸部の断面形状（高さ及び／又は幅）を変更した。 [Comparative Examples 1 and 2]
A heat-generating film was produced by the same method as in Example 1 except that the size of the pattern A on the Si wafer used as a mold was changed. The distance between the convex portions in the first direction and / or the second direction of the Si wafer, and the cross-sectional shape (height and / or width) of the convex portions so that the patterns of the sizes shown in Table 3 are formed on the transparent film. Changed.
［比較例３及び４］
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図９に示すパターンＦが形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。パターンＦは、所謂、ライン／スペース（Ｌ／Ｓ）パターンであり、第１方向に延び、表３に示す線幅及び高さを有するライン（導電部）を表３に示すスペース（第１間隔Ｐ１）で配置した。 [Comparative Examples 3 and 4]
The same method as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern F shown in FIG. 9 is formed by a linear convex portion having a rectangular cross section on one surface is used as a mold. Manufactured a heat-generating film. The pattern F is a so-called line / space (L / S) pattern, in which a line (conductive portion) extending in the first direction and having the line width and height shown in Table 3 is represented by a space (first interval) shown in Table 3. It was arranged in P1).
モールドとして、一方の表面に断面形状が矩形の線状の凸部により、図９に示すパターンＦが形成されているＳｉウエハ（３００ｍｍ×３００ｍｍ）を用いた以外は、実施例１と同様の方法により発熱フィルムを製造した。パターンＦは、所謂、ライン／スペース（Ｌ／Ｓ）パターンであり、第１方向に延び、表３に示す線幅及び高さを有するライン（導電部）を表３に示すスペース（第１間隔Ｐ１）で配置した。 [Comparative Examples 3 and 4]
The same method as in Example 1 except that a Si wafer (300 mm × 300 mm) in which the pattern F shown in FIG. 9 is formed by a linear convex portion having a rectangular cross section on one surface is used as a mold. Manufactured a heat-generating film. The pattern F is a so-called line / space (L / S) pattern, in which a line (conductive portion) extending in the first direction and having the line width and height shown in Table 3 is represented by a space (first interval) shown in Table 3. It was arranged in P1).
実施例１～１６及び比較例１～４で得られた発熱フィルムについて、導電部の線幅Ｗ及び高さＨ、第１導電部間の第１間隔Ｐ１、第２導電部間の第２間隔Ｐ２を測定した。また、導電部の形成する各パターンにおける、導電部の面積比率、交点の数及び断線影響面積を計算した。結果を表１～３に示す。
Regarding the heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4, the line width W and height H of the conductive portions, the first interval P1 between the first conductive portions, and the second interval between the second conductive portions P2 was measured. In addition, the area ratio of the conductive portion, the number of intersections, and the area affected by disconnection in each pattern formed by the conductive portion were calculated. The results are shown in Tables 1 to 3.
［発熱フィルムの特性の評価］
＜電気特性評価試験＞
実施例１～１６及び比較例１～４で得られた発熱フィルムを用い、導電部が形成されている表面側の電気特性を抵抗評価装置（三菱ケミカルアナリテック社製の商品名「ロレスタ‐ＧＸ」）を用いて四探針法で計測し、面抵抗値を求めた。このようにして求めた面抵抗値を表１～３に示す。 [Evaluation of heat-generating film characteristics]
<Electrical characterization test>
Using the heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4, a resistance evaluation device (trade name "Loresta-GX" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) is used to evaluate the electrical characteristics of the surface side on which the conductive portion is formed. The surface resistance value was determined by measuring with the four-probe method using "). The surface resistance values obtained in this way are shown in Tables 1 to 3.
＜電気特性評価試験＞
実施例１～１６及び比較例１～４で得られた発熱フィルムを用い、導電部が形成されている表面側の電気特性を抵抗評価装置（三菱ケミカルアナリテック社製の商品名「ロレスタ‐ＧＸ」）を用いて四探針法で計測し、面抵抗値を求めた。このようにして求めた面抵抗値を表１～３に示す。 [Evaluation of heat-generating film characteristics]
<Electrical characterization test>
Using the heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4, a resistance evaluation device (trade name "Loresta-GX" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) is used to evaluate the electrical characteristics of the surface side on which the conductive portion is formed. The surface resistance value was determined by measuring with the four-probe method using "). The surface resistance values obtained in this way are shown in Tables 1 to 3.
＜透明性評価試験＞
実施例１～１６及び比較例１～４で得られた発熱フィルムについて、次のようにして透明性を評価した。分光光度計（日立ハイテクノロジーズ社製の商品名「日立分光光度計Ｕ－４１００」）を用い、各発熱フィルムに波長５５０ｎｍの光を照射して透過率を測定した。測定結果を表１及び２に示す。 <Transparency evaluation test>
The heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were evaluated for transparency as follows. Using a spectrophotometer (trade name "Hitachi Spectrophotometer U-4100" manufactured by Hitachi High-Technologies Corporation), each heat generating film was irradiated with light having a wavelength of 550 nm to measure the transmittance. The measurement results are shown in Tables 1 and 2.
実施例１～１６及び比較例１～４で得られた発熱フィルムについて、次のようにして透明性を評価した。分光光度計（日立ハイテクノロジーズ社製の商品名「日立分光光度計Ｕ－４１００」）を用い、各発熱フィルムに波長５５０ｎｍの光を照射して透過率を測定した。測定結果を表１及び２に示す。 <Transparency evaluation test>
The heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were evaluated for transparency as follows. Using a spectrophotometer (trade name "Hitachi Spectrophotometer U-4100" manufactured by Hitachi High-Technologies Corporation), each heat generating film was irradiated with light having a wavelength of 550 nm to measure the transmittance. The measurement results are shown in Tables 1 and 2.
＜骨見え評価試験＞
実施例１～１６及び比較例１～４で得られた発熱フィルムについて、４００ｌｕｘの蛍光灯環境下で発熱フィルムの外観を目視にて検査し、以下の基準で配線の骨見えを評価した。測定結果を表１～３に示す。 <Bone appearance evaluation test>
With respect to the heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4, the appearance of the heat-generating films was visually inspected under a fluorescent lamp environment of 400 lux, and the appearance of the wiring was evaluated according to the following criteria. The measurement results are shown in Tables 1 to 3.
実施例１～１６及び比較例１～４で得られた発熱フィルムについて、４００ｌｕｘの蛍光灯環境下で発熱フィルムの外観を目視にて検査し、以下の基準で配線の骨見えを評価した。測定結果を表１～３に示す。 <Bone appearance evaluation test>
With respect to the heat-generating films obtained in Examples 1 to 16 and Comparative Examples 1 to 4, the appearance of the heat-generating films was visually inspected under a fluorescent lamp environment of 400 lux, and the appearance of the wiring was evaluated according to the following criteria. The measurement results are shown in Tables 1 to 3.
＜骨見えの評価基準＞
◎：３０ｃｍ離れた正面および斜めからでも配線が視認できない
〇：３０ｃｍ離れた正面から観察して配線が視認できないが、斜めから観察すると配線が視認できる
△：３０ｃｍ離れた正面から観察して配線がはっきり視認できる
×：５０ｃｍ離れた正面から観察して配線がはっきり視認できる <Evaluation criteria for bone visibility>
⊚: Wiring cannot be seen even from the front and diagonally 30 cm away 〇: Wiring cannot be seen when observed from the front 30 cm away, but wiring can be seen when observed from an angle △: Wiring can be seen when observed from the front 30 cm away Clearly visible ×: Wiring can be clearly seen by observing from the front 50 cm away.
◎：３０ｃｍ離れた正面および斜めからでも配線が視認できない
〇：３０ｃｍ離れた正面から観察して配線が視認できないが、斜めから観察すると配線が視認できる
△：３０ｃｍ離れた正面から観察して配線がはっきり視認できる
×：５０ｃｍ離れた正面から観察して配線がはっきり視認できる <Evaluation criteria for bone visibility>
⊚: Wiring cannot be seen even from the front and diagonally 30 cm away 〇: Wiring cannot be seen when observed from the front 30 cm away, but wiring can be seen when observed from an angle △: Wiring can be seen when observed from the front 30 cm away Clearly visible ×: Wiring can be clearly seen by observing from the front 50 cm away.
実施例１～１６の発熱フィルムは、導電部の骨見えが抑制されており、透過率（透明性）が高かった。また、面抵抗値が特定の範囲内（０．００３～７０Ω／ｓｑ．）にあることから、通電時に十分な発熱量が得られることがわかった。また、交点の数が特定の範囲内（２０～２５００個／ｃｍ２）であることから、導電部の断線の影響を受け難く、耐久性及び信頼性が高いことがわかった。
In the heat-generating films of Examples 1 to 16, the appearance of bones in the conductive portion was suppressed, and the transmittance (transparency) was high. Further, since the surface resistance value is within a specific range (0.003 to 70Ω / sq.), It was found that a sufficient amount of heat can be obtained when energized. Further, since the number of intersections was within a specific range (20 to 2500 / cm 2 ), it was found that the number of intersections was not easily affected by the disconnection of the conductive portion, and the durability and reliability were high.
また、線幅が７μｍとやや大きい実施例１０の発熱フィルムは、線幅が１～３μｍの他の実施例と比較して、導電部の骨見えがやや目立った（骨見え評価結果：△）。また、格子パターンとして同じパターンＡを用いた実施例１～１１、１４及び１５を比較する。導電部の線幅Ｗが２μｍ以下であり、第１間隔Ｐ１が３００μｍ未満であり、第２間隔Ｐ２が１０００～５０００μｍ以下である実施例１、３、６及び７は、導電部の骨見えがより抑制されており（骨見え評価結果：◎）、且つ透過率も高かった。
Further, in the heat-generating film of Example 10 having a slightly large line width of 7 μm, the bone visibility of the conductive portion was slightly conspicuous as compared with other Examples having a line width of 1 to 3 μm (bone appearance evaluation result: Δ). .. In addition, Examples 1 to 11, 14 and 15 using the same pattern A as the lattice pattern are compared. In Examples 1, 3, 6 and 7 in which the line width W of the conductive portion is 2 μm or less, the first interval P1 is less than 300 μm, and the second interval P2 is 1000 to 5000 μm or less, the bones of the conductive portion are visible. It was more suppressed (bone appearance evaluation result: ⊚), and the transmittance was also high.
一方、比較例１は、第１間隔Ｐ１が１４９８μｍと大きく、且つ交点数が１３個／ｃｍ２と少ないため、断線影響面積が７．５ｍｍ２と大きかった。この結果から、比較例１の発熱フィルムは、導電部の断線の影響を受け易く、耐久性及び信頼性が低いことがわかった。比較例２は、導電部の線幅が１５μｍと大きいため、骨見えが顕著であった（骨見え評価結果：×）。比較例３は、線幅が５５μｍと大きく、また、Ｌ／Ｓパターン（パターンＦ）であるため交点を有さず、断線影響面積が７２８ｍｍ２と大きかった。このため、比較例３の発熱フィルムは、骨見えが顕著であり（骨見え評価結果：×）、また、導電部の断線の影響を受け易く、耐久性及び信頼性が低いことがわかった。また、比較例４は、Ｌ／Ｓパターンであるが線幅が細いため骨見えは抑制できたが（骨見え評価：◎）、交点を有さず、断線影響面積が１５ｍｍ２と大きいため、導電部の断線の影響を受け易く、耐久性及び信頼性が低いことがわかった。
On the other hand, in Comparative Example 1, since the first interval P1 was as large as 1498 μm and the number of intersections was as small as 13 / cm 2 , the area affected by disconnection was as large as 7.5 mm 2. From this result, it was found that the heat-generating film of Comparative Example 1 was easily affected by the disconnection of the conductive portion and had low durability and reliability. In Comparative Example 2, since the line width of the conductive portion was as large as 15 μm, the bone visibility was remarkable (bone visibility evaluation result: ×). In Comparative Example 3, the line width was as large as 55 μm, and since it was an L / S pattern (pattern F), there were no intersections, and the area affected by disconnection was as large as 728 mm 2. Therefore, it was found that the heat-generating film of Comparative Example 3 had remarkable bone visibility (bone visibility evaluation result: ×), was easily affected by disconnection of the conductive portion, and had low durability and reliability. Further, in Comparative Example 4, although it was an L / S pattern, the bone visibility could be suppressed because the line width was narrow (bone visibility evaluation: ⊚), but there was no intersection and the area affected by the disconnection was as large as 15 mm 2. It was found that it was easily affected by the disconnection of the conductive part and had low durability and reliability.
＜発熱特性試験＞
実施例６、７及び比較例４で得られた発熱フィルムについて、以下の方法により、昇温速度を測定した。１０ｃｍ角にカットした発熱フィルム（試料）の端部表面に、第１方向に電流を流すための接続電極として、１０ｃｍの長さの線状電極を銀ペーストにより形成した。これにより、接続電極は約１０ｃｍの間隔をあけて配置された。発熱フィルム（試料）を－１０℃の恒温槽の中に投入し、接続電極の間に５Ｖの電圧を４０秒印加した。電圧印加前後のサンプルの温度をサンプルに張り付けた熱電対によって測定した。発熱フィルムの電圧印加前後の温度差（上昇温度）を印加時間である４０秒で割り、発熱フィルムの昇温速度とした。 <Heat generation characteristic test>
The heating rate of the heat-generating films obtained in Examples 6 and 7 and Comparative Example 4 was measured by the following method. A linear electrode having a length of 10 cm was formed of silver paste on the end surface of a heat-generating film (sample) cut into 10 cm squares as a connection electrode for passing an electric current in the first direction. As a result, the connection electrodes were arranged at intervals of about 10 cm. The heat-generating film (sample) was placed in a constant temperature bath at −10 ° C., and a voltage of 5 V was applied between the connection electrodes for 40 seconds. The temperature of the sample before and after applying the voltage was measured by a thermocouple attached to the sample. The temperature difference (rising temperature) before and after applying the voltage of the heat-generating film was divided by the application time of 40 seconds to obtain the heating rate of the heat-generating film.
実施例６、７及び比較例４で得られた発熱フィルムについて、以下の方法により、昇温速度を測定した。１０ｃｍ角にカットした発熱フィルム（試料）の端部表面に、第１方向に電流を流すための接続電極として、１０ｃｍの長さの線状電極を銀ペーストにより形成した。これにより、接続電極は約１０ｃｍの間隔をあけて配置された。発熱フィルム（試料）を－１０℃の恒温槽の中に投入し、接続電極の間に５Ｖの電圧を４０秒印加した。電圧印加前後のサンプルの温度をサンプルに張り付けた熱電対によって測定した。発熱フィルムの電圧印加前後の温度差（上昇温度）を印加時間である４０秒で割り、発熱フィルムの昇温速度とした。 <Heat generation characteristic test>
The heating rate of the heat-generating films obtained in Examples 6 and 7 and Comparative Example 4 was measured by the following method. A linear electrode having a length of 10 cm was formed of silver paste on the end surface of a heat-generating film (sample) cut into 10 cm squares as a connection electrode for passing an electric current in the first direction. As a result, the connection electrodes were arranged at intervals of about 10 cm. The heat-generating film (sample) was placed in a constant temperature bath at −10 ° C., and a voltage of 5 V was applied between the connection electrodes for 40 seconds. The temperature of the sample before and after applying the voltage was measured by a thermocouple attached to the sample. The temperature difference (rising temperature) before and after applying the voltage of the heat-generating film was divided by the application time of 40 seconds to obtain the heating rate of the heat-generating film.
実施例６の発熱フィルムの昇温速度は０．０７℃／ｓｅｃ.であり、実施例７の発熱フィルムの昇温速度は０．０４℃／ｓｅｃ.であった。これらの値は発熱フィルムとして十分な昇温速度であり、実施例５及び７の発熱フィルムが十分な発熱特性を有していることが確認できた。
The heating rate of the heat-generating film of Example 6 was 0.07 ° C./sec., And the heating rate of the heat-generating film of Example 7 was 0.04 ° C./sec. These values were sufficient heating rates for the heat-generating film, and it was confirmed that the heat-generating films of Examples 5 and 7 had sufficient heat-generating characteristics.
一方、比較例４で得られた発熱フィルムは、試験の途中で導電部に断線が発生し、昇温速度を測定することができなかった。
On the other hand, in the heat-generating film obtained in Comparative Example 4, the conductive portion was broken during the test, and the temperature rising rate could not be measured.
本発明の発熱フィルムは、導電部の骨見えを抑制でき、透明性（透過率）が高く、また、通電時に十分な発熱量を得られる。それゆえ、車両の運転者の視界及び車両の意匠性を低下させずに、車両の窓、ミラー等を効率的に加熱できる発熱フィルムとして利用できる。
The heat-generating film of the present invention can suppress the appearance of bones in the conductive portion, has high transparency (transmittance), and can obtain a sufficient amount of heat generation when energized. Therefore, it can be used as a heat-generating film that can efficiently heat the windows, mirrors, etc. of the vehicle without deteriorating the visibility of the driver of the vehicle and the design of the vehicle.
１０ 発熱フィルム
１１ 透明フィルム
１１ｓ 透明フィルム表面
１１ｃ 凹部（溝）
１２ 透明樹脂層
１３ 導電部
１３Ａ 第１導電部
１３Ｂ 第２導電部
Ｒ 交点
２０ モールド
２０ａ モールド凸部
２８ 下地層
３３ 透明支持基材 10 Heat-generatingfilm 11 Transparent film 11s Transparent film surface 11c Recess (groove)
12Transparent resin layer 13 Conductive part 13A 1st conductive part 13B 2nd conductive part R intersection 20 Mold 20a Mold convex part 28 Base layer 33 Transparent support base material
１１ 透明フィルム
１１ｓ 透明フィルム表面
１１ｃ 凹部（溝）
１２ 透明樹脂層
１３ 導電部
１３Ａ 第１導電部
１３Ｂ 第２導電部
Ｒ 交点
２０ モールド
２０ａ モールド凸部
２８ 下地層
３３ 透明支持基材 10 Heat-generating
12
Claims (13)
- 発熱フィルムであって、
表面に第１方向に延在する複数の第１溝と、第１方向と交差する第２方向に延在する複数の第２溝とを有する透明フィルムと、
第１及び第２の溝内に存在する導電部とを備え、
前記導電部の線幅が０．２～１０μｍであり、
前記導電部の高さが、０．５～１０μｍであり、
隣り合う２つの第１溝内に存在する前記導電部間の間隔が、２０～１０００μｍであり、
第１溝内に存在する前記導電部と、第２溝内に存在する前記導電部との交点の数が、２０～２５００個／ｃｍ２であり、
前記導電部の面積比率が０．１～１０％である発熱フィルム。 It ’s a heat-generating film,
A transparent film having a plurality of first grooves extending in the first direction on the surface and a plurality of second grooves extending in the second direction intersecting the first direction.
It is provided with a conductive portion existing in the first and second grooves, and is provided with a conductive portion.
The line width of the conductive portion is 0.2 to 10 μm, and the line width is 0.2 to 10 μm.
The height of the conductive portion is 0.5 to 10 μm.
The distance between the conductive portions existing in the two adjacent first grooves is 20 to 1000 μm.
The number of intersections between the conductive portion existing in the first groove and the conductive portion existing in the second groove is 20 to 2500 pieces / cm 2 .
A heat-generating film having an area ratio of the conductive portion of 0.1 to 10%. - 前記発熱フィルムの、波長５５０ｎｍにおける光の透過率が、６０～９８％である請求項１に記載の発熱フィルム。 The heat-generating film according to claim 1, wherein the heat-generating film has a light transmittance of 60 to 98% at a wavelength of 550 nm.
- 前記発熱フィルムの面抵抗値が０．００３～７０Ω／ｓｑ．である請求項１又は２に記載の発熱フィルム。 The surface resistance value of the heat-generating film is 0.003 to 70Ω / sq. The heat-generating film according to claim 1 or 2.
- 第１方向における、隣り合う２つの第２溝内に存在する前記導電部間の間隔が１０００～１５０００μｍである請求項１～３のいずれか一項に記載の発熱フィルム。 The heat-generating film according to any one of claims 1 to 3, wherein the distance between the conductive portions existing in two adjacent second grooves in the first direction is 1000 to 15000 μm.
- 第２方向が第１方向と直交する請求項１～４のいずれか一項に記載の発熱フィルム。 The heat-generating film according to any one of claims 1 to 4, wherein the second direction is orthogonal to the first direction.
- 複数の第１溝内に存在する導電部から構成される第１複線部を複数備え、
隣り合う２つの第１複線部は、２０～１０００μｍの第１間隔で配置され、
第１複線部を構成する前記複数の導電部は、第１間隔より小さい第４間隔で配置されている請求項１～５のいずれか一項に記載の発熱フィルム。 A plurality of first double-track portions composed of conductive portions existing in a plurality of first grooves are provided.
The two adjacent first double-track sections are arranged at a first spacing of 20 to 1000 μm.
The heat-generating film according to any one of claims 1 to 5, wherein the plurality of conductive portions constituting the first double-track portion are arranged at a fourth interval smaller than the first interval. - 第４間隔が、０．２～２０μｍである請求項６に記載の発熱フィルム。 The heat-generating film according to claim 6, wherein the fourth interval is 0.2 to 20 μm.
- 複数の第２溝内に存在する導電部から構成される第２複線部を複数備え、
隣り合う２つの第２複線部は、第１方向において第２間隔で配置され、
第２複線部を構成する前記複数の導電部は、第１方向において第２間隔より小さい第５間隔で配置されている請求項１～７のいずれか一項に記載の発熱フィルム。 A plurality of second double-track portions composed of conductive portions existing in a plurality of second grooves are provided.
Two adjacent second double-track sections are arranged at a second spacing in the first direction.
The heat-generating film according to any one of claims 1 to 7, wherein the plurality of conductive portions constituting the second double-track portion are arranged at a fifth interval smaller than the second interval in the first direction. - 第５間隔が、０．５～２０μｍである請求項８に記載の発熱フィルム。 The heat-generating film according to claim 8, wherein the fifth interval is 0.5 to 20 μm.
- 請求項１～９のいずれか一項に記載の発熱フィルムの製造方法であって、
表面に、第１溝及び第２溝を有する前記透明フィルムを用意することと、
第１溝及び第２溝に導電性材料を充填して、前記導電部を形成することとを含む発熱フィルムの製造方法。 The method for producing a heat-generating film according to any one of claims 1 to 9.
To prepare the transparent film having the first groove and the second groove on the surface, and to prepare the transparent film.
A method for producing a heat-generating film, which comprises filling the first groove and the second groove with a conductive material to form the conductive portion. - 前記透明フィルムを用意することが、前記導電部に対応する凹凸パターンを有するモールドを用いたインプリントにより、前記透明フィルム上に第１溝及び第２溝を形成することを含む請求項１０に記載の発熱フィルムの製造方法。 The tenth aspect of the present invention, wherein preparing the transparent film includes forming a first groove and a second groove on the transparent film by imprinting using a mold having a concavo-convex pattern corresponding to the conductive portion. Method of manufacturing heat-generating film.
- 前記透明フィルムが、透明支持基材と、透明支持基材上に形成された透明樹脂層とを有し、
前記透明フィルムを用意することが、
前記導電部に対応する凹凸パターンを有する前記モールドを用意することと、
前記モールドの前記凹凸パターンが形成された表面に、光硬化性の樹脂を塗布して塗布層を形成することと、
前記塗布層上に、前記透明支持基材を配置することと、
前記透明支持基材側から紫外線の光を照射して前記塗布層を硬化させ、前記透明樹脂層を形成することと、
前記透明樹脂層から前記モールドを剥離することとを含む請求項１１に記載の発熱フィルムの製造方法。 The transparent film has a transparent support base material and a transparent resin layer formed on the transparent support base material.
To prepare the transparent film
To prepare the mold having a concavo-convex pattern corresponding to the conductive portion,
A photocurable resin is applied to the surface of the mold on which the uneven pattern is formed to form a coating layer.
By arranging the transparent support base material on the coating layer,
By irradiating the transparent support base material side with ultraviolet light to cure the coating layer, the transparent resin layer is formed.
The method for producing a heat-generating film according to claim 11, which comprises peeling the mold from the transparent resin layer. - 無電解メッキにより前記導電部を形成する請求項１０～１２のいずれか一項に記載の発熱フィルムの製造方法。 The method for producing a heat-generating film according to any one of claims 10 to 12, wherein the conductive portion is formed by electroless plating.
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| JP2020018819A JP2021125395A (en) | 2020-02-06 | 2020-02-06 | Heat-generating film, and method for manufacturing method thereof |
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| CN114550980A (en) * | 2022-03-08 | 2022-05-27 | 苏州兴派丽智能科技有限公司 | Conductive film, preparation method thereof and display device |
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| JPH08207191A (en) * | 1995-02-06 | 1996-08-13 | Nippon Oil Co Ltd | Heating element and reticulated structure therefor |
| JP2015020723A (en) * | 2013-07-23 | 2015-02-02 | 大日本印刷株式会社 | Glass device for vehicle |
| JP2017010679A (en) * | 2015-06-18 | 2017-01-12 | 大日本印刷株式会社 | Windows with transparent heating plate and transparent heating plate |
| JP2018039226A (en) * | 2016-09-09 | 2018-03-15 | リンテック株式会社 | Ice and snow attachment prevention sheet |
| JP2018055941A (en) * | 2016-09-28 | 2018-04-05 | 大日本印刷株式会社 | Heating conductor, sheet with conductor, heating plate and vehicle |
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2020
- 2020-02-06 JP JP2020018819A patent/JP2021125395A/en active Pending
-
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- 2021-02-01 WO PCT/JP2021/003560 patent/WO2021157532A1/en active Application Filing
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| JPH08207191A (en) * | 1995-02-06 | 1996-08-13 | Nippon Oil Co Ltd | Heating element and reticulated structure therefor |
| JP2015020723A (en) * | 2013-07-23 | 2015-02-02 | 大日本印刷株式会社 | Glass device for vehicle |
| JP2017010679A (en) * | 2015-06-18 | 2017-01-12 | 大日本印刷株式会社 | Windows with transparent heating plate and transparent heating plate |
| JP2018039226A (en) * | 2016-09-09 | 2018-03-15 | リンテック株式会社 | Ice and snow attachment prevention sheet |
| JP2018055941A (en) * | 2016-09-28 | 2018-04-05 | 大日本印刷株式会社 | Heating conductor, sheet with conductor, heating plate and vehicle |
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| CN114550980A (en) * | 2022-03-08 | 2022-05-27 | 苏州兴派丽智能科技有限公司 | Conductive film, preparation method thereof and display device |
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