WO2020149113A1 - Film électroconducteur transparent - Google Patents

Film électroconducteur transparent Download PDF

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Publication number
WO2020149113A1
WO2020149113A1 PCT/JP2019/050485 JP2019050485W WO2020149113A1 WO 2020149113 A1 WO2020149113 A1 WO 2020149113A1 JP 2019050485 W JP2019050485 W JP 2019050485W WO 2020149113 A1 WO2020149113 A1 WO 2020149113A1
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Prior art keywords
transparent
transparent conductive
conductive film
film
conductive
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PCT/JP2019/050485
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English (en)
Japanese (ja)
Inventor
西澤　剛
由克 水野
隆志 岡部
本間　敬之
Original Assignee
Ｊｘｔｇエネルギー株式会社
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Priority to JP2020566173A priority Critical patent/JPWO2020149113A1/ja
Publication of WO2020149113A1 publication Critical patent/WO2020149113A1/fr

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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a transparent conductive film.
  • Transparent conductive films are used for display devices such as flat-screen TVs, mobile phones, smartphones, tablets, touch panels, solar cells, electroluminescent elements, electromagnetic shields, and functional glass.
  • Indium tin oxide hereinafter abbreviated as ITO
  • ITO Indium tin oxide
  • Patent Document 1 discloses a conductive film that uses a conductive nanowire network. Since the nanowires forming this conductive nanowire network have an average width of 1.5 ⁇ m or less, the nanowire network is difficult to see, but since silver is used, there is a problem that migration easily occurs.
  • Patent Document 2 by the present applicant discloses a method for producing a metal mold having a random network structure using nanofibers, and producing a transparent conductive film having a conductive portion having a random network structure using the metal mold. ing.
  • an object of the present invention is to provide a transparent conductive film that does not use ITO and that has a conductive portion that has excellent transparency, low resistance, and high adhesion to the transparent film.
  • a transparent film on the surface of which linear grooves are formed in a predetermined pattern With a conductive portion filled in the groove, The line width W of the conductive portion exposed from the groove is the same as the line width of the groove and is in the range of 200 to 2000 nm (0.2 to 2 ⁇ m), There is provided a transparent conductive film, wherein a ratio H/W of a height H of the conductive portion to a line width W of the conductive portion is 1 to 5.
  • the predetermined pattern of the transparent conductive film is a regular pattern having intersection points of straight lines or curved lines, and voids may exist at the intersection points of the lattice.
  • the predetermined pattern of the transparent conductive film may be a grid pattern.
  • the width of the void P of the transparent conductive film may be 0.6 times or more the line width W of the groove of the conductive portion.
  • the height H of the conductive portion of the transparent conductive film may be higher than the depth D of the groove by 0 to 500 nm (0 to 0.5 ⁇ m).
  • the conductive part of the transparent conductive film may be partially filled in the groove.
  • the ratio H/D of the height H of the conductive portion to the depth D of the groove may be higher than 0.1 and lower than 1.
  • the cross-sectional shape of the groove of the transparent conductive film may be rectangular.
  • the transparent conductive film may further include a lead wiring formed on the transparent film, and the lead wiring may be electrically connected to the conductive portions formed in the plurality of predetermined regions.
  • the transmittance of light having a wavelength of 550 nm may be 70% or more, and the sheet resistance may be 0.1 to 10 ⁇ /sq.
  • the transparent conductive film of the present invention is a substitute material for the ITO film, but the ratio of the height to the width of the conductive portion (aspect ratio) is large, and the conductive portion does not extend beyond the groove width (does not protrude), Both transparency and low resistance can be achieved. Since the conductive portion has high adhesion to the transparent film and the transparent conductive film has high bending resistance, it has excellent durability even in applications where stress is generated on the film surface during operation of a touch panel or the like. Therefore, the transparent conductive film of the present invention can be suitably used for various devices such as touch panels, electronic papers, and thin film solar cells.
  • FIG. 1A is a view conceptually showing the cross-sectional structure of the transparent conductive film of the embodiment
  • FIG. 1B shows an enlarged cross-sectional structure near the conductive portion 13 shown in FIG. 1A. It is a figure. It is a figure which shows notionally the planar structure of the transparent conductive film of embodiment.
  • FIG. 3A is a view showing another embodiment in which the conductive portion 13 projects from the film surface 11s
  • FIG. 3B shows another embodiment in which the conductive portion 13 is partially filled in the convex portion 11c. It is a figure which shows a form.
  • FIG. 4(a) to 4(d) are views conceptually showing a step of manufacturing a transparent substrate including a resin layer 22 having lattice-shaped concave portions 11c formed on the surface thereof in the method of manufacturing a transparent conductive film.
  • 5A to 5C are views conceptually showing steps required for electroless plating in the method for producing a transparent conductive film.
  • 1 is a photograph of a surface of a transparent conductive film obtained in Example 1 on which a copper conductive layer is formed in a recess, observed with a laser microscope.
  • 3 is a photograph of a cross section of a recess of the transparent conductive film obtained in Example 1, observed with a scanning electron microscope.
  • FIG. 8A is a view showing a cut portion at the intersection of the lattice pattern of the transparent conductive film obtained in Example 1, and FIG. 8B is cut at the cut portion of FIG. 8A.
  • 2 is a photograph of the cross section observed with a scanning electron microscope.
  • FIG. 9 is a photograph in which the transparent conductive film obtained in Example 2 was tilted at 45° and the recesses were observed with a scanning electron microscope.
  • FIG. 10 is a photograph in which the transparent conductive film obtained in Example 3 was tilted at 45° and the recesses were observed with a scanning electron microscope.
  • FIG. 11 is a photograph of a cross section of the recess of the transparent conductive film obtained in Comparative Example 1, observed with a scanning electron microscope.
  • FIG. 12 is a diagram conceptually showing a modified example of the planar structure of the transparent conductive film, and the conductive portion has a simulation pattern in which sine curves are orthogonal to each other at intersections.
  • the transparent conductive film 10 of the present embodiment includes a transparent film 11 composed of a transparent support substrate 33 and a transparent resin layer 12 formed thereon, and a transparent film 11 on the transparent film 11. And a conductive portion 13 formed on.
  • a recess 11c having a rectangular cross section is formed in the transparent resin layer 12, and the conductive portion 13 is formed by filling the recess 11c with a conductive material.
  • the recess 11 c has a grid pattern in a plan view of the transparent conductive film 10
  • the conductive portion 13 has a grid pattern in which a plurality of line portions 13 e are regularly orthogonal to each other.
  • the transparent film 11 has the transparent support substrate 33 and the transparent resin layer 12 laminated thereon.
  • the transparent resin layer 12 may be made of a photocurable resin, a thermosetting resin, a moisture curable resin, a chemically curable resin (mixed with two liquids) or the like. 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, cross-linked liquid crystal-based, fluorine-based, silicone-based , Various resins such as polyamide-based monomers, oligomers and polymers.
  • the thickness of the transparent resin layer 12 may be in the range of 0.5 to 500 ⁇ m.
  • the thickness is less than the lower limit, the depth of the concave portion 11c formed in the transparent resin layer 12 tends to be insufficient, and if it exceeds the upper limit, there is a concern that the influence of the volume change of the resin generated during curing becomes large.
  • the transparent support substrate 33 a known film substrate that transmits visible light can be used.
  • a substrate 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,
  • 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 (a polyimide resin, a polyimideamide resin or the like), a cycloolefin polymer or the like can be used.
  • the transparent support substrate 33 may be a resin film.
  • the thickness of the transparent supporting substrate 33 is preferably 1 to 500 ⁇ m from the viewpoint of optical characteristics.
  • the conductive portion 13 (line portion 13e) is formed so as to fill the concave portion (groove) 11c of the transparent film 11, and is formed outside the concave portion 11c in the in-plane direction of the film. It does not stick out.
  • the surface 11s of the transparent film 11 means the surface portion of the transparent film 11 excluding the concave portion 11c.
  • 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 (a portion higher than the surface of the transparent film 11) may be present. Nevertheless, the raised portion 13x does not protrude outside the recess 11c in the in-plane direction of the substrate. By doing so, the cross-sectional area of the conductive portion 13 forming the metal wiring can be increased, and as a result, the resistance value of the metal wiring can be reduced without increasing the coverage of the film surface of the metal wiring.
  • the height of the raised portion 13x (height from the surface 11s) is 0.5 ⁇ m or less, preferably 0.3 ⁇ m or less. If it exceeds 0.5 ⁇ m, the abrasion resistance of the conductive portion is reduced.
  • H/D When expressed as the ratio of the height H of the conductive portion 13 to the depth D of the recess 11c, H/D is 1.0 ⁇ H/D ⁇ 1.2, particularly 1. It is preferable that 0 ⁇ H/D ⁇ 1.1 (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 in the recess 11c.
  • the height H of the conductive portion 13 is preferably at least 0.02 ⁇ m or more in order to ensure conductivity. If it is less than 0.02 ⁇ m, the conductivity may be insufficient.
  • the line width W is the width of the line portion 13e in a cross section perpendicular to the direction in which the line portion 13e extends (simply referred to as "the line width of the conductive portion").
  • the line portion 13e does not necessarily have to be a straight line, and curves such as a sine curve may intersect each other to form the intersection R (see FIG. 12). Since the line portions 13e are orthogonal to each other, the line portions are evenly distributed in a plan view, and transparency is improved.
  • the width W of the line portion 13e of the conductive portion 13 may be in the range of 200 to 3000 nm, preferably 200 to 2000 nm, more preferably 200 to 1500 nm, and particularly preferably 200 to 1200 nm. When the line width W exceeds 3000 nm, the conductive portion 13 may be visible. When the line width W is less than 200 nm, the conductivity of the conductive portion 13 may be insufficient.
  • the coverage of the transparent film 11 by the conductive portion 13 may be in the range of 0.3% to 15%, more preferably 0.6% to 8%, and particularly preferably 0.8% to 7.8%. desirable.
  • the coverage is less than 0.3%, the conductivity of the transparent conductive film 10 may be insufficient. If the coverage exceeds 15%, the transparency (transmittance) of the transparent conductive film 10 may be insufficient.
  • the transparency of the transparent conductive film 10 is expressed by a transmittance, for example, 70% or more is preferable, 75% or more is more preferable, and 78% or more is particularly preferable for light having a wavelength of 550 nm.
  • the height H of the line portion 13e of the conductive portion 13 (hereinafter, simply referred to as "height H of the conductive portion 13") is 1 times the line width W of the conductive portion 13. It is above, and preferably 1 to 5 times.
  • the ratio of the height H of the conductive portion 13 to the line width W of the conductive portion 13 is appropriately referred to as “aspect ratio" in this document. That is, the aspect ratio of the cross-sectional shape in the plane perpendicular to the extending direction of the conductive portion 13 is preferably in the range of 1:1 to 5:1, more preferably 1:1 to 3:1.
  • the conductive portion 13 of the present embodiment Since the height H of the conductive portion 13 of the present embodiment is 1 time or more the line width W, the conductive portion 13 has a line width W of 3000 nm or less for the purpose of improving transparency. 13 can have sufficient conductivity. Thereby, the transparent conductive film 10 can have both good appearance (visibility) and high conductivity. With such a configuration, the transparent conductive film 10 has a low surface resistance (sheet) of 0.1 to 80 ⁇ /sq, preferably 0.1 to 50 ⁇ /sq, more preferably 0.1 to 10 ⁇ /sq. Resistance). Further, when the height H of the conductive portion 13 is larger than 5 times the line width W, the visibility may decrease when the transparent conductive film 10 is viewed obliquely.
  • the height ratio of the intersection R where the line 13e intersects is equal to or smaller than the height H of the line 13e.
  • a void P exists in the conductive material filled in each intersection R (see FIG. 8).
  • the void P is generated in the vicinity of the bottom of the recess 11c, and is 0.05 to 50% of the volume of the intersection R, or 5% in the cross section obtained by cutting the intersection R at an angle of 45° with respect to the line portion 13e. Occupies the above cross-sectional area.
  • the cross-sectional area of the void P is 60% or more of the cross-sectional area of the recess 11 when observed with the cross-sectional area of the inclined cut surface, as in Examples described later.
  • the width of the void P is 0.3 times or more the line width W, and particularly preferably 0.5 to 1.0.
  • the width of the void is the average width in the line width direction, and the average width here is the width at three points of the bottom (lower surface), opening surface (upper surface) and half height of the groove. Use the average value.
  • the inventor believes that the voids are generated as follows. Metal deposits from the side surface of the groove during plating. Here, since the distance in the diagonal direction of the intersection R is longer than the width of the line portion 13e, if the metal deposition is stopped when the wiring portion is filled, the metal deposition is interrupted at the intersection R. Voids will likely occur.
  • 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 compounds of these metals are preferable, and from the viewpoint of flexibility, metals or alloys such as silver and copper are preferable.
  • the transparent conductive film 10 may be provided with a lead wiring connected to the end of the conductive portion 13 for use in various applications such as a touch panel.
  • the lead-out wiring may have 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 materials as those exemplified as the material of the conductive portion 13 can be used.
  • the transparent conductive film 10 for example, a mold having a concave-convex pattern corresponding to the conductive portion 13 is used, a transparent film base material with concave-convex is formed by imprint, and then the concave portion is filled with a conductive member by electroless plating. It can be produced by Hereinafter, a specific example of the method for manufacturing the transparent conductive film 10a will be described with reference to FIGS.
  • a mold 20 with a concavo-convex pattern in which rectangular convex portions 20a having a cross-sectional shape are formed at predetermined intervals on the surface is prepared.
  • the concavo-convex pattern of the mold is a grid-like pattern in which a plurality of straight line portions intersect at a predetermined interval in a plan view (see the pattern in FIG. 2).
  • the height and width of the convex portions 20a and the interval between the convex portions 20a are set to be the same as the design size of the conductive portion 13 described above.
  • the mold 20 can be manufactured by, for example, a photolithography method in which a photoresist applied on a silicon substrate is exposed to light and etched through a mask having a predetermined pattern.
  • a mold release agent is preferably applied to the surface of the mold 20 for the next step.
  • a photo-curable resin such as an ultraviolet curable resin is applied to the surface of the mold 20 on which the convex portions 20a are formed to form the resin layer 22.
  • the thickness of the resin layer 22 may be, for example, 10 to 50 ⁇ m.
  • a film (transparent support base) 24 made of a synthetic resin such as a PET film is arranged on the resin layer 22 to form a laminate as shown in FIG. 4(b).
  • the thickness of the film 24 may be about 50 to 200 ⁇ m.
  • this laminate is irradiated with ultraviolet light from the film 24 side to cure the photocurable resin forming the resin layer 22.
  • the mold 20 is peeled off from the resin layer 12 of the laminated body, and the resin layer 22 having the lattice-shaped concave portions 11c corresponding to the pattern of the convex portions 20a of the mold formed on the surface thereof.
  • a transparent substrate (transparent film) 30 having Next, as shown in FIG. 4D, a protective film 26 is attached to the lower surface of the film 24 (the surface opposite to the resin layer 22). The protective film 26 protects the surface of the resin layer 22 in the steps up to electroless plating, and is peeled off later.
  • the conductive portion 13 was formed by electroless plating as follows.
  • silane coupling treatment When performing electroless plating, it is preferable to perform a silane coupling treatment on the site where the plating film is applied in order to secure a strong adhesion of the plating film.
  • the silane coupling agent used for such treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, 3-( Aminosilane compounds such as N-phenyl)aminopropyltrimethoxysilane and other silane compounds having a reactive functional group can be used.
  • the underlayer 28 is formed on the surface of the resin layer 22 including the recess 11c as shown in FIG. 5A. ..
  • the transparent substrate 30 may be heated after being taken out of the solution. Further, before immersing the transparent substrate 30 in the solution of the underlayer forming material, the surface of the resin layer 22 may be irradiated with UV light to modify the surface of the resin layer 22.
  • processing is performed so that the underlayer 22 exists only on the inner surface of the recess 11c.
  • UV light can be applied only to the underlayer 28 on the surface of the resin layer 22 excluding the opening of the recess 11c.
  • a mask that blocks light may be used.
  • FIG. 5B it is possible to obtain the transparent substrate 30 in which the underlayer 28 exists only on the inner surface of the recess 11c.
  • the transparent substrate 30 having the underlying layer 28 only on the inner surface of the recess 11c obtained as described above is dipped in a known plating catalyst liquid to form the recess 11c.
  • a substrate precursor of a plating substrate in which palladium ions are supported only inside is obtained.
  • the plating catalyst liquid a palladium (II) chloride solution or a tetrachloride gold (III) acid solution can be used. Further, by subjecting this substrate to a reduction treatment, a transparent substrate (plating precursor) having a plating catalyst such as palladium attached only to the inner surface of the recess 11c can be obtained.
  • Example 1 Transparent substrate preparation process
  • linear protrusions with a rectangular cross-section (height 1.4 ⁇ m, width 1.0 ⁇ m) were arranged on one surface at intervals of 25 ⁇ m (spacing from the center of one protrusion to the center of adjacent protrusions).
  • a Si wafer 300 mm ⁇ 300 mm having a grid-like pattern extending in the vertical direction and the horizontal direction and intersecting with each other was prepared (see FIG. 4A).
  • a mold release treatment was performed by forming a film of a fluorine-based precision mold release agent (ultra-thin film having a thickness of about 30 nm) on the surface having the protrusions.
  • UV curable resin An acrylic UV curable resin (hereinafter, simply referred to as “UV curable resin” in some cases) was drop cast on the mold surface subjected to the mold release treatment to form a resin layer made of the UV curable resin with a thickness of 13 ⁇ m. Then, a PET film having a thickness of 100 ⁇ m was placed on the resin layer, and a resin layer made of a UV curable resin was sandwiched between the mold and the PET film to obtain a laminate (see FIG. 4B). Next, this laminate was irradiated with UV light having a center wavelength of 365 nm from the PET film side at 2000 mJ/cm 2 using a high pressure mercury lamp to cure the UV curable resin forming the resin layer.
  • the mold was peeled off from the resin layer of the laminate to obtain a transparent substrate having a resin layer on the surface of which lattice-shaped concave portions derived from the pattern shape of the convex portions of the mold were formed (see FIG. 4C). ).
  • a protective film was attached to the surface of the PET film of the transparent substrate thus obtained (see FIG. 4(d)).
  • the intervals (pitch) P between the recesses of the transparent substrate were all 25 ⁇ m, the cross-sectional shape of the recesses was rectangular, the width of the recesses was 1.0 ⁇ m, and the depth of the recesses was 1.4 ⁇ m. ..
  • An underlayer raw material solution used for the silane coupling treatment was prepared as follows. 70 mL of 3-aminopropyltriethoxysilane was added to 930 mL of ethanol, and the mixture was stirred for 5 hours. Then, the liquid temperature was raised to 55° C. using an oil bath to obtain a solution of 3-aminopropyltriethoxysilane (base layer raw material solution).
  • the entire surface of the resin layer-side surface of the transparent substrate with a protective film obtained as described above was irradiated with UV light at 3000 mJ/cm 2 to preliminarily modify the surface of the resin layer. Then, using an oil bath, while maintaining the liquid temperature of the underlayer raw material solution at 55° C., the transparent substrate with the protective film after surface modification was immersed in this solution, and the ultrasonic cleaning machine was used at 40 kHz. A cleaning process of applying ultrasonic waves for 20 minutes was performed.
  • an underlayer made of 3-aminopropyltriethoxysilane (the 3-aminopropyl which is the material of the underlayer) is formed on the entire surface on the resin layer side (the entire surface including the inner surface of the recess).
  • a layer consisting of a reaction product of triethoxysilane and a hydroxyl group on the substrate was formed.
  • the transparent substrate on which the underlayer was formed was taken out from the solution of 3-aminopropyltriethoxysilane, and then 3-aminopropyltriethoxysilane was formed on the entire surface of the substrate on the resin layer side of the transparent substrate and the inner surface of the recess.
  • the transparent substrate was subjected to a heat treatment for 10 minutes in an oven heated to 70° C. so that the layer made of was more sufficiently adhered. Then, the transparent substrate after the heat treatment is immersed in 1 L of ethanol under the condition of room temperature (25° C.), and ultrasonic waves are applied for 10 minutes at 40 kHz using an ultrasonic cleaner, so that excess 3 -Aminopropyltriethoxysilane was removed. In this way, a transparent substrate was obtained in which a base layer made of 3-aminopropyltriethoxysilane was formed over the entire surface of the transparent substrate on the resin layer side and the inner surface of the recess (FIG. )reference).
  • UV light was applied to the entire surface of the underlayer-side surface of the transparent substrate on which the underlayer was formed, and the underlayer existing near the substrate surface was removed from the substrate surface and the inner surface of the recess.
  • a base layer is present on the inner surface of the recess except for the vicinity of the substrate surface. That is, a transparent substrate was obtained in which the underlayer was selectively formed only on the inner surface of the concave portion of the substrate.
  • the precursor of the transparent substrate for plating is washed with ion-exchanged water and then immersed in 1 L of ion-exchanged water in a reducing solution (treatment solution containing a reducing agent) in which 3.0 g of dimethylamine borane is dissolved. Then, the ultrasonic wave was applied at 170 kHz for 20 minutes using an ultrasonic cleaner. In this way, by reducing the palladium ions selectively supported in the recesses in the precursor of the plating substrate to form metal palladium, the catalyst layer made of metal palladium is selectively supported inside the recesses. The obtained transparent substrate for plating 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: 100ppm 2,2'-Bipyridyl: 10ppm Sodium hydroxide: the amount added to bring the pH to 12.5 to 13.2 Residual: deionized water
  • the protective film from the transparent substrate for plating After removing the protective film from the transparent substrate for plating, it was immersed in an electroless plating solution in a plating bath and subjected to electroless plating under the conditions of temperature: 60° C. and time: 20 minutes. Then, it was washed with pure water and dried. The copper plating film was formed only inside the recess of the transparent substrate for plating. Thus, a transparent conductive film in which a metal conductive layer made of copper was formed inside the recess was obtained. The coverage of the transparent substrate for plating (transparent film) by the metal conductive layer (conductive portion) was 7.8%.
  • Example 2 An Si wafer similar to that of Example 1 was prepared except that the height of the convex portions was 2.0 ⁇ m, and a transparent substrate for plating on which an underlayer and a catalyst layer were selectively formed was prepared as in Example 1. Obtained. Using this plating substrate, the electroless copper plating time was changed to 30 minutes, and a transparent conductive film was produced in the same manner as in Example 1. In the obtained transparent conductive film, the metal conductive layer (copper plating film) filled the inside of the recess, and further became a slightly raised layer as shown in FIG. 3(a).
  • Example 3 An Si wafer similar to that of Example 1 was prepared except that the height of the convex portions was 2.0 ⁇ m, and a transparent substrate for plating on which an underlayer and a catalyst layer were selectively formed was prepared as in Example 1. Obtained. Using this plating substrate, the electroless copper plating time was changed to 10 minutes, and a transparent conductive film was produced in the same manner as in Example 1. In the obtained transparent conductive film, the metal conductive layer (copper plating film) was a layer formed so as to fill about 80% of the inside of the recess as shown in FIG. 3B.
  • Example 1 An Si wafer similar to that in Example 1 was prepared except that the height of the convex portion was 2.0 ⁇ m, and a transparent substrate on which an underlayer was formed was prepared in the same manner as in Example 1. Instead of irradiating UV light only to the surface of the base layer side of this substrate, this substrate was immersed in an alkaline aqueous solution (pH 12) at 80° C., and thereafter, catalyst loading and electroless copper plating were performed as in Example 1. A transparent conductive film was prepared.
  • an alkaline aqueous solution pH 12
  • the metal conductive layer (copper plating film) is not formed so as to completely fill the inside of the recess, and further protrudes from the frame of the recess (groove) and covers the substrate surface in the vicinity of the recess (groove). It had been.
  • the width is 1.0 ⁇ m
  • the height (thickness) is It was found that it was in the range of 1.1 ⁇ m (lowest part) to 1.4 ⁇ m (highest part) (the aspect ratio was in the range of 1.1 to 1.4).
  • Fig. 8(b) shows a photograph of the cross section of the intersection of the grid pattern.
  • the cross section of the intersecting portion was cut obliquely (angle is about 21 degrees) with respect to the straight line portion of the lattice as shown in “Cross section observation point” in FIG.
  • the void P exists on the bottom side and the front side of the central portion of the recess.
  • the width of the void P was about 0.7 ⁇ m.
  • the metal conductive layer of the transparent conductive film of Example 2 filled the recesses (grooves) and was further raised from the substrate surface (in the photograph, a portion with an oval mark). That is, the metal conductive layer (copper plated film) has a shape that follows the shape of the inside of the recess, has a W width of 1.0 ⁇ m, and is 0.1 ⁇ m (lowermost portion) than the substrate surface. It was found to have a convex portion having a height in the range of up to 0.4 ⁇ m (highest portion) (see the raised portion 13x in FIG. 3A). In addition, it was found that, in the central portion of the metal conductive layer at the intersection of the grid-like patterns, a void P having no conductive material was present in the central portion of the metal conductive layer as in the transparent conductive film of Example 1. It was found that, in the central portion of the metal conductive layer at the intersection of the grid-like patterns, a void P having no conductive material was present in the central portion of
  • the metal conductive layer of the transparent conductive film of Example 3 filled only a part of the recess (groove) (in the photograph of FIG. 10, a portion indicated by an oval).
  • the object existing near the upper right of the oval mark (substrate surface) in Fig. 10 is a foreign substance attached to the film surface). That is, the metal conductive layer (copper plating film) has a shape along the shape of the inside of the recess, the width thereof is 1.0 ⁇ m, and the height thereof is 0.2 to 0 than that of the substrate surface. It was found to be low in the range of 0.3 ⁇ m.
  • a void P having no conductive material was present in the central portion of the metal conductive layer as in the transparent conductive film of Example 1. It was found that, in the central portion of the metal conductive layer at the intersection of the grid-like patterns, a void P having no conductive material was present in the central portion of the metal conductive layer as in the transparent conductive film of Example 1. It was found that, in the central
  • the metal conductive layer of the transparent conductive film of Comparative Example 1 is formed along the recess (groove) as shown in FIG. 11, but it can be seen that the central part is not completely filled.
  • the metal conductive layer is formed so as to protrude from the concave portion and spread over the surface of the substrate.
  • the metal conductive layer was slightly present on the bottom surface of the recess at the center of the metal conductive layer at the intersection of the grid pattern, and the void P without the metal conductive layer was not present. Note that in FIG. 11, the opening of the recess is widened and deformed, but this is the deformation that occurred during the cross-section processing of the sample for observation with the scanning electron microscope.
  • the transparent conductive films of Examples 1 to 3 and Comparative Example 1 all had sufficiently small resistance values and were capable of passing a good current with a low load.
  • the surface resistance value of the transparent conductive film of Example 2 is particularly low because the copper plating rises up above the concave portion without spreading in the in-plane direction of the substrate surface, resulting in the volume of the conductive portion. It is thought that this is due to the increase in.
  • the transparent conductive film of Example 3 it is considered that the volume of the conductive portion was reduced because the conductive material was only partially filled in the recess.
  • the transparent conductive films obtained in Examples 1 to 3 and Comparative Example 1 were subjected to a bending resistance evaluation test by the following method.
  • the transparent conductive film is pressed from a metal rod having a diameter of 6 mm on the surface of the transparent conductive film having no metal conductive layer, and the transparent conductive film is supported from both ends so that the surface of the PET film adheres along the arc of the metal rod.
  • the bending test was performed. After bending the transparent conductive film in this manner, the surface resistance value was measured by the same method as in the above-described electrical characteristic evaluation test.
  • Table 2 shows the increase rate (change rate) of the sheet resistance value after the bending test with respect to the sheet resistance value before the bending test. When there is no change, it is calculated to be 100%.
  • the transparent conductive films of Examples 1 to 3 had a transmittance of monochromatic light having a wavelength of 550 nm of 78% or more, which was higher than that of the transparent conductive film of Comparative Example 1.
  • the conductive member was present in the recesses of the substrate in a plan view, whereas in the transparent conductive films of Comparative Example 1, outside the recesses of the substrate in a plan view, That is, it is considered that this is because the conductive member protrudes from the recess in the in-plane direction of the substrate. From this test result, it can be said that the transparent conductive films of Examples 1 to 3 have sufficiently high transparency.
  • a transparent conductive film having a conductive portion of a grid pattern that periodically crosses in the vertical and horizontal directions in a plan view was produced, but the present invention is not limited to this, and the conductive portion has various conductive patterns that are orthogonal at intersections.
  • It may be a transparent conductive film having a part.
  • it may be a periodic pattern in which curved lines such as sine curves intersect each other vertically and horizontally in plan view.
  • FIG. 12 shows a pattern in which the pitch (linear interval) of the conductive portions is 100 ⁇ m, the sine curve period is 200 ⁇ m, the amplitude (one side) is 20 ⁇ m, and the line width is 1 ⁇ m, but any pattern in the range of 10 to 1000 ⁇ m can be used. It can be pitch (sine curve period is twice the pitch, amplitude (one side) is less than half the pitch).
  • the pattern of the conductive portion as shown in FIG. 12 can be formed by using the above-mentioned imprint method by producing a mold in which convex portions having the same pattern are formed. In addition to the sine curve, if the intersecting portions are orthogonal to each other, an arbitrary linear pattern, for example, a pattern in which a plurality of circles are overlapped can be formed.
  • the transparent conductive film and the metal mold of the present invention and the manufacturing methods thereof are not limited to the above embodiments, and are within the scope of the technical idea described in the claims. Can be modified appropriately.
  • the transparent conductive film of the present invention has high transparency, can sufficiently withstand bending and rubbing, and has a low surface resistance value. Therefore, the transparent conductive film of the present invention can be suitably used for various devices such as touch panels, electronic papers, and thin film solar cells.
  • Transparent conductive film 11 Transparent film 11s Transparent film surface 11c Recess (groove) 12 Transparent Resin Layer 13 Conductive Part 13e Conductive Part Line 13s Conductive Part Surface 13x Conductive Part Raised Part R Intersection 20 Mold 20a Mold Convex Part 22 Resin Layer 24 Film 26 Protective Film 28 Underlayer 30 Transparent Substrate 33 Transparent Supporting Base Material

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  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
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Abstract

Film électroconducteur transparent présentant une transparence élevée, une faible résistance et une adhésivité élevée à un film transparent d'une partie électroconductrice. Ce film électroconducteur transparent 10 comprend un film transparent 11 sur la surface duquel des sections renfoncées linéaires 11c sont formées selon un motif prescrit, et des parties électroconductrices 13 avec lesquelles les sections renfoncées sont remplies, la largeur W des parties électroconductrices 13 qui est exposée à partir des sections renfoncées 11c étant la même que la largeur des sections évidées et étant en outre dans une plage de 200 à 2000 nm, et le rapport H/W de la hauteur H sur la largeur W des parties électroconductrices 13 étant de 1 à 5. Les parties électroconductrices 13 ne font pas saillie dans la direction dans le plan d'une surface 11s de film.
PCT/JP2019/050485 2019-01-17 2019-12-24 Film électroconducteur transparent WO2020149113A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021200434A1 (fr) * 2020-03-31 2021-10-07 Ｅｎｅｏｓ株式会社 Film électroconducteur transparent et procédé de fabrication de film électroconducteur transparent
WO2023022175A1 (fr) * 2021-08-17 2023-02-23 Tdk株式会社 Film électriquement conducteur et son procédé de fabrication, et dispositif d'affichage
WO2024004537A1 (fr) * 2022-06-29 2024-01-04 パナソニックＩｐマネジメント株式会社 Motif d'électrode et capteur tactile l'utilisant

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2009090915A1 (fr) * 2008-01-17 2009-07-23 Nichia Corporation Procédé de production d'un matériau conducteur, matériau conducteur obtenu grâce au procédé, dispositif électronique contenant le matériau conducteur, dispositif électroluminescent, et procédé de fabrication d'un dispositif électroluminescent
WO2011096244A1 (fr) * 2010-02-08 2011-08-11 コニカミノルタホールディングス株式会社 Procédé de fabrication de substrat électroconducteur transparent, substrat électroconducteur transparent obtenu, et élément d'afficheur
WO2017163832A1 (fr) * 2016-03-24 2017-09-28 Ｊｘエネルギー株式会社 Film conducteur transparent, procédé de fabrication de film conducteur transparent, moule métallique et procédé de fabrication de moule métallique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009090915A1 (fr) * 2008-01-17 2009-07-23 Nichia Corporation Procédé de production d'un matériau conducteur, matériau conducteur obtenu grâce au procédé, dispositif électronique contenant le matériau conducteur, dispositif électroluminescent, et procédé de fabrication d'un dispositif électroluminescent
WO2011096244A1 (fr) * 2010-02-08 2011-08-11 コニカミノルタホールディングス株式会社 Procédé de fabrication de substrat électroconducteur transparent, substrat électroconducteur transparent obtenu, et élément d'afficheur
WO2017163832A1 (fr) * 2016-03-24 2017-09-28 Ｊｘエネルギー株式会社 Film conducteur transparent, procédé de fabrication de film conducteur transparent, moule métallique et procédé de fabrication de moule métallique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021200434A1 (fr) * 2020-03-31 2021-10-07 Ｅｎｅｏｓ株式会社 Film électroconducteur transparent et procédé de fabrication de film électroconducteur transparent
WO2023022175A1 (fr) * 2021-08-17 2023-02-23 Tdk株式会社 Film électriquement conducteur et son procédé de fabrication, et dispositif d'affichage
WO2024004537A1 (fr) * 2022-06-29 2024-01-04 パナソニックＩｐマネジメント株式会社 Motif d'électrode et capteur tactile l'utilisant

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