WO2019049617A1 - Film conducteur, capteur de panneau tactile et panneau tactile - Google Patents

Film conducteur, capteur de panneau tactile et panneau tactile Download PDF

Info

Publication number
WO2019049617A1
WO2019049617A1 PCT/JP2018/030305 JP2018030305W WO2019049617A1 WO 2019049617 A1 WO2019049617 A1 WO 2019049617A1 JP 2018030305 W JP2018030305 W JP 2018030305W WO 2019049617 A1 WO2019049617 A1 WO 2019049617A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
metal
conductive
layer
substrate
Prior art date
Application number
PCT/JP2018/030305
Other languages
English (en)
Japanese (ja)
Inventor
孝彦 一木
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2019049617A1 publication Critical patent/WO2019049617A1/fr

Links

Images

Classifications

    • 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
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • 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

Definitions

  • the present invention relates to a conductive film, a touch panel sensor, and a touch panel.
  • substrate is used for various uses. For example, in recent years, with the increase in the loading rate of touch panels on mobile phones, portable game devices, etc., the demand for conductive films for capacitive touch panel sensors capable of multipoint detection is rapidly expanding.
  • the user looks at the display from a distance of several tens of centimeters from the display.
  • it is required to further narrow the line width of the thin metal wire.
  • thin metal wires having a narrow line width have poor adhesion to the substrate.
  • a conductive film provided with a layer having a function of further improving the adhesion between the substrate and the fine metal wire.
  • Patent Document 1 discloses a transparent conductive film provided with a transparent electrode layer having a fine metal wire pattern on at least one surface of a transparent film substrate, and the fine metal wire is A second metal layer in contact with the first metal layer and the first metal layer from the transparent film substrate side in this order, and a Ni base metal layer is mainly provided between the transparent film substrate and the first metal layer A transparent conductive film is described, wherein the base metal layer and the first metal layer are in contact with each other.
  • Patent Document 1 The inventor examined the transparent conductive film described in Patent Document 1.
  • the line width of the metal fine wire is 2.0 ⁇ m or less, the metal fine wire becomes the base metal when exposed to the atmosphere for a long time It has been found that the problem of peeling from the substrate as a whole and the problem of peeling between the first metal layer and the base metal layer tend to occur.
  • this invention makes it a subject to provide the conductive film containing a metal fine wire whose line
  • Another object of the present invention is to provide a touch panel sensor and a touch panel including the above-mentioned conductive film.
  • the present inventors have found that the above problems can be solved by the conductive film in which the side surface portion of the base layer mainly composed of nickel alone is covered with a predetermined film.
  • the present invention has been completed. That is, it discovered that the said objective could be achieved by the following structures.
  • a conductive film comprising: a substrate; and a conductive portion composed of fine metal wires disposed on at least one of the main surfaces of the substrate,
  • the metal fine wire includes an underlayer and a conductive layer disposed in this order from the substrate side, and a film covering the side surface of the underlayer, and the line width is 2.0 ⁇ m or less.
  • the base layer contains nickel alone as a main component
  • the conductive layer contains copper as a main component
  • the conductive film, wherein the film contains a metal selected from metals which are electrochemically nobler than nickel, and whose thickness is less than 100 nm.
  • the conductive film according to [1] wherein the film contains a metal selected from metals electrochemically nobler than silver.
  • [3] The conductive film according to [1] or [2], wherein the film contains palladium.
  • [4] The conductive film according to any one of [1] to [3], wherein the line width of the fine metal wire is 1.2 ⁇ m or less.
  • [5] The conductive film according to any one of [1] to [4], wherein the conductive layer contains copper in an amount of 90% by mass or more based on the total mass of the layer.
  • a touch panel sensor comprising the conductive film according to any one of [1] to [5].
  • [7] A touch panel including the touch panel sensor according to [6].
  • a conductive film including a metal fine wire having a line width of 2.0 ⁇ m or less and excellent in adhesion to a substrate over a long period of time it is possible to provide a touch panel sensor and a touch panel including the above-mentioned conductive film.
  • FIG. 3 is a cross-sectional view taken along the line AA of the conductive film shown in FIG. 2A. It is a partially expanded view of the electroconductive part in FIG. 2A. It is a fragmentary sectional view of 1st Embodiment of the electroconductive film of this invention (it is sectional drawing in the BB cross section in FIG. 2C). It is a fragmentary sectional view of a 2nd embodiment of a conductive film of the present invention. It is a fragmentary sectional view of a substrate with a foundation film obtained by performing a foundation film formation process.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • active light or “radiation” in the present specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV: extreme ultraviolet lithography) light, X-rays, and Means electron beam etc.
  • light means actinic rays and radiation.
  • the "exposure” in the present specification means not only exposure by far ultraviolet rays represented by a mercury lamp and an excimer laser, X-rays and EUV light but also particle beams such as electron beams and ion beams unless otherwise specified. Also includes drawing by.
  • the feature of the conductive film of the present invention is that the side portion of the base layer containing a single nickel as a main component is covered with a predetermined film.
  • Patent Document 1 As shown in FIG. 1, a metal thin wire 108 provided with a substrate 100, a base metal layer 102 disposed on the substrate 100, a first metal layer 104, and a second metal layer 106. And a transparent conductive film 110 is disclosed.
  • the base metal layer 102 contains nickel as a main component.
  • the metal fine wire 108 peels off from the substrate 100 together with the base metal layer 102 when exposed to the atmosphere for a long time.
  • the metal fine wire 108 peels off from the substrate 100 together with the base metal layer 102 when exposed to the atmosphere for a long time.
  • the inventor found that the above problem is that nickel, which is the main component of the base metal layer 102, is easily corroded in the presence of oxygen and water in the atmosphere, starting from the side surface portion 102a exposed to the atmosphere. I speculated that it was the cause.
  • the corrosion of the base metal layer 102 mainly composed of nickel proceeds to the inside of the base metal layer 102 depending on the time of exposure to the atmosphere.
  • the adhesion of the base metal layer 102 to the substrate 100 is lowered and the adhesion of the base metal layer 102 to the first metal layer 104 is lowered.
  • the line width L1 of the metal thin wire 108 is an ultra thin wire having a width of 2.0 ⁇ m or less, the influence of corrosion starting from the side surface portion 102a of the base metal layer 102 becomes relatively large. Becomes more prominent.
  • the present invention which solved the above-mentioned problem is explained, taking the specific embodiment as an example.
  • the feature of the conductive film of the present invention is that the side portion of the base layer containing nickel alone as the main component is covered with a predetermined film.
  • the fine metal wires 12 disposed on the substrate 10 are the underlayer 14 disposed in this order from the substrate 10 side.
  • the line width L2 of the thin metal wire 12 is 2.0 ⁇ m or less.
  • the underlayer 14 contains a single nickel as a main component, and the film 18 contains a metal selected from metals which are electrochemically nobler than nickel.
  • electrochemically noble metal than nickel intends metal whose ionization tendency is lower than that of nickel, for example, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, iridium, Platinum and gold can be mentioned. That is, the side layer portion 14a of the underlayer 14 is covered with a metal material which is less susceptible to corrosion than nickel in the presence of oxygen and water in the atmosphere, whereby the underlayer 14 is made in the presence of oxygen and water in the atmosphere. The corrosion that occurs is suppressed.
  • the thickness L3 of the film 18 needs to be less than 100 nm.
  • the thickness L3 of the film 18 is 100 nm or more, the contact surface of the underlayer 14 with the substrate 10 becomes relatively smaller, and the adhesion of the underlayer 14 to the substrate 10 is lowered.
  • the line width of the thin metal wire is relatively large (for example, about 3 to 10 ⁇ m), the decrease in adhesion depending on the thickness of the film is not observed.
  • the fine metal wires 32 disposed on the substrate 10 are the underlayer 34 disposed in this order from the substrate 10 side. And the conductive layer 36, and the film 38 covering the side portion 34a of the base layer 34.
  • the conductive layer 36 is disposed on the surface 34b formed of the base layer 34 and the film 38 covering the side surface portion 34a.
  • the metal thin line 32 has a line width L4 of 2.0 ⁇ m or less.
  • the base layer 34 contains a simple substance of nickel as a main component
  • the film 38 contains a metal selected from metals which are electrochemically nobler than nickel.
  • the base layer 34 is inhibited from being corroded in the presence of oxygen and water in the air.
  • the thickness L5 of the film 38 is less than 100 nm.
  • the contact surface of the underlayer 34 with the substrate 10 becomes relatively small, and the adhesion of the underlayer 34 to the substrate 10 is lowered. It has been confirmed that when the line width of the thin metal wire is relatively large (for example, about 3 to 10 ⁇ m), the decrease in adhesion depending on the thickness of the film is not observed.
  • FIG. 2A is a top view of the first embodiment of the conductive film of the present invention
  • FIG. 2B is a cross-sectional view of the conductive film shown in FIG. 2A, taken along the line AA.
  • FIG. 2C is a partially enlarged view of the conductive portion in FIG. 2A.
  • the conductive film 20 of the present invention includes a substrate 10 and a conductive portion 13 disposed on at least one of the main surfaces of the substrate 10 as shown in FIGS. 2A and 2B.
  • the type of the substrate 10 is not particularly limited as long as the substrate 10 has a main surface and supports the conductive portion 13.
  • a flexible substrate preferably an insulating substrate
  • a resin substrate is more preferable.
  • the substrate 10 preferably transmits 60% or more of visible light (wavelength 400 to 800 nm) light, more preferably transmits 80% or more, still more preferably 90% or more, and transmits 95% or more. Is particularly preferred.
  • the material constituting the resin substrate examples include polyether sulfone resins, polyacrylic resins, polyurethane resins, polyester resins (polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate resins, polysulfone resins, polyamide resins Examples thereof include resins, polyarylate resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, and cycloolefin resins. Among them, cycloolefin resins are preferable in that they have more excellent optical properties.
  • the thickness of the substrate 10 is not particularly limited, but is preferably 0.01 to 0.5 mm, more preferably 0.03 to 0.2 mm, from the viewpoint of balance between handleability and thinning.
  • the substrate 10 may have a multilayer structure, and may include, for example, a functional film as one of its layers. The substrate itself may be a functional film.
  • the conductive film may have a three-dimensional shape (three-dimensional shape).
  • the three-dimensional shape include a three-dimensional shape including a curved surface, and more specifically, a hemispherical shape, a semicylindrical shape, a corrugated shape, a convex-concave shape, and a cylindrical shape.
  • the electroconductive part 13 is arrange
  • the conductive portions 13 may be disposed on both main surfaces of the substrate 10.
  • the conductive part 13 is arrange
  • positioning pattern may be sufficient.
  • FIG. 2C is a partially enlarged top view of the conductive portion 13.
  • the conductive portion 13 is formed of a plurality of thin metal wires 12 and includes a mesh-like pattern including a plurality of openings T formed by the crossing thin metal wires 12.
  • the line width of the thin metal wire 12 is 2.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and still more preferably 1.2 ⁇ m or less.
  • the lower limit of the line width of the thin metal wire 12 is not particularly limited, but generally 0.2 ⁇ m or more is preferable. For example, when the conductive film is applied to a touch panel sensor, if the line width of the metal thin wire 12 is 2.0 ⁇ m or less, it is more difficult for the user of the touch panel to visually recognize the metal thin wire.
  • the thickness of the thin metal wire 12 is not particularly limited, but generally 0.1 to 5.0 ⁇ m is preferable, and 0.2 to 2.0 ⁇ m is more preferable from the viewpoint of conductivity.
  • the length X of one side of the opening T is preferably 20 to 250 ⁇ m.
  • the opening T has a substantially rhombus shape.
  • polygonal shapes for example, triangles, quadrangles, hexagons, and random polygons.
  • the shape of one side may be a curved shape or an arc shape other than a linear shape.
  • the two opposing sides may have an outwardly convex arc shape, and the other two opposing sides may have an inward convex arc shape.
  • the shape of each side may be a wavy line shape in which an outward convex arc and an inward convex arc are continuous.
  • the shape of each side may be a sine curve.
  • the electroconductive part 13 has a mesh-like pattern, it is not restrict
  • FIG. 3 is a partial cross-sectional view of the conductive film 20 (corresponding to a cross-sectional view taken along a line BB in FIG. 2C).
  • the metal thin wire 12 includes the base layer 14 and the conductive layer 16 disposed in this order from the substrate 10 side, and the film 18 covering the periphery of the base layer 14 and the conductive layer 16. Further, as described above, the line width L2 of the thin metal wire 12 is 2.0 ⁇ m or less.
  • the line width of the thin metal wire 12 can be obtained by embedding the thin metal wire 12 together with the substrate 10 in a resin and cutting it with an ultramicrotome in the width direction (direction orthogonal to the extending direction of the thin metal wire 12). After depositing carbon on the cross section, a line width measured by observing with a scanning electron microscope (S-5500 manufactured by Hitachi High-Technologies Corporation) is intended. When the line width differs in the height direction, the largest measurement width is defined as the line width.
  • the underlayer 14 contains a single nickel as a main component.
  • the said main component intends the component with largest content (mass) among the components contained in the base layer 14.
  • unit in the foundation layer 14 Generally 60 mass% or more is preferable with respect to the foundation layer total mass, and 70 mass% or more is more preferable.
  • the upper limit is not particularly limited, but is 100% by mass.
  • the underlayer 14 has a conductive property and also has a function of improving the adhesion between the substrate 10 and the conductive layer 16. It does not restrict
  • the thickness of the underlayer 14 is not particularly limited, but is preferably 5 nm or more. When the thickness of the base layer 14 is in the above numerical range, the metal thin wire 12 is more excellent in adhesion to the substrate 10.
  • the upper limit of the thickness of the underlayer 14 is not particularly limited, and is, for example, 50 nm or less.
  • the conductive layer 16 contains copper as a main component.
  • the conductive layer 16 functions as a conductive portion of the thin metal wire 12.
  • the conductive layer 16 contains copper or an alloy thereof, but the main component is copper, and it is preferable that the content of copper is 90% by mass or more with respect to the total mass of the conductive layer in that the conductivity is more excellent.
  • the main component is intended to mean the metal having the largest content (mass) of the metals contained in the conductive layer 16.
  • the upper limit of the content of copper in the conductive layer 16 is not particularly limited, and is, for example, 100% by mass with respect to the total mass of the conductive layer.
  • the thickness of the conductive layer 16 is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, and still more preferably 1.0 ⁇ m or less.
  • the lower limit of the thickness of the conductive layer 16 is not particularly limited, but in general, 0.1 ⁇ m or more is preferable.
  • the conductive layer 16 may be a single layer or multiple layers. When the conductive layer 16 is a single layer, it can be formed, for example, by sputtering or vapor deposition. Still, when the conductive layer 16 is a multilayer, the conductive layer 16 is, for example, a seed layer formed by a sputtering method, a vapor deposition method, or an electroless plating method in that the conductivity of the metal fine wire 12 is more excellent; It is preferable to have the plating layer arrange
  • the thickness of the seed layer is not particularly limited, but in general, 300 nm or less is preferable.
  • the lower limit of the thickness of the seed layer is not particularly limited, but generally 30 nm or more is preferable.
  • the thickness of the plating layer is not particularly limited, but generally 3.0 ⁇ m or less is preferable, 2.0 ⁇ m or less is more preferable, and 1.0 ⁇ m or less is still more preferable.
  • the lower limit of the thickness of the plating layer is not particularly limited, but in general, 0.1 ⁇ m or more is preferable.
  • the seed layer may include, for example, metals such as copper, nickel, chromium, lead, gold, silver, tin, and zinc, and alloys of these metals.
  • the main component (so-called, main metal) contained in the seed layer is preferably a metal other than nickel, and examples thereof include copper, chromium, lead, gold, silver, tin and zinc.
  • the said main component intends metal whose content (mass) is the largest among metals contained in the said seed layer.
  • the seed layer preferably contains copper or an alloy thereof, in that the seed layer is superior in affinity to the plating layer and / or in that the function as a seed layer is more excellent.
  • the main component of the seed layer is preferably copper.
  • the content of the metal constituting the main component in the seed layer is not particularly limited, but generally, the content of the metal is preferably 80% by mass or more, and more preferably 85% by mass or more based on the total mass of the seed layer. .
  • the said plating layer As a metal contained in the said plating layer, copper or its alloy is preferable. As a main component (so-called, main metal) contained in the said plating layer, copper is preferable. In addition, the said main component intends the metal with largest content (mass) among the metals contained in the said plating layer.
  • the content of copper constituting the main component in the plating layer is not particularly limited, but generally, the content of the metal is preferably 80% by mass or more, more preferably 90% by mass or more based on the total mass of the plating layer. Preferably, 100% by mass is more preferable.
  • the film 18 contains a metal selected from metals which are electrochemically nobler than nickel, and has a thickness L3 of less than 100 nm.
  • the metal selected from metals which are electrochemically more noble than nickel is intended to be a metal whose ionization tendency is lower than that of nickel, for example, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, iridium, platinum , And gold.
  • the film 18 preferably contains a metal selected from metals which are electrochemically nobler than silver, in that the adhesion of the fine metal wire 12 to the substrate 10 is excellent over a long period of time, and the visibility is further improved by blackening. It is more preferable to contain palladium in that the effect is also obtained.
  • the film 18 contains a metal selected from metals which are more electrochemically noble than nickel.
  • the main component is intended to be the component having the largest content (mass) among the components contained in the film 18.
  • the content of the metal selected from the metals which are electrochemically more noble than nickel in the film 18 is not particularly limited, but generally, the content of the metal is 80% by mass or more based on the total mass of the film 18 Is preferable, 90 mass% or more is more preferable, and 100 mass% is still more preferable.
  • the film 18 preferably contains a metal other than silver.
  • the thickness L3 (see FIG. 3) of the film 18 is less than 100 nm.
  • the metal selected from metals electrochemically nobler than nickel contained in the film 18 has poor adhesion to the substrate 10 as compared to nickel.
  • the thickness L3 of the film 18 is 100 nm or more, the contact surface of the underlayer 14 with the substrate 10 is relatively reduced, and the adhesion of the underlayer 14 to the substrate 10 is reduced. 70 nm or less is preferable and 50 nm or less is more preferable at the point which the adhesiveness of the base layer 14 with respect to the board
  • the lower limit of the thickness L3 of the film 18 is, for example, 10 nm or more.
  • the thickness L3 of the film 18 is preferably 20 nm or more, in that the adhesion of the thin metal wire 12 to the substrate 10 is excellent over a long period of time.
  • the thickness L3 of the film 18 is intended to be a thickness obtained by elemental mapping using an EDS (Energy dispersive X-ray spectrometry) detector. Specifically, the thickness L3 of the film 18 is measured by the following method.
  • C (carbon) vapor deposition and Pt coating are performed on the conductive portion of the conductive film to impart conductivity and protect the surface.
  • the metal thin wire is cut in the width direction (direction orthogonal to the extending direction of the metal thin wire) using a Helios 400 type FIB-SEM (FIB: Focused Ion Beam, SEM: Scanning Electron Microscope) composite machine manufactured by FEI.
  • FIB-SEM Focused Ion Beam
  • SEM Scanning Electron Microscope
  • the formation method of the film 18 is not particularly limited, and a known formation method can be used, and among them, the substitution blackening treatment method is preferable.
  • the substitutional blackening treatment is a reaction utilizing the difference in ionization tendency among metals. According to the substitutional blackening treatment method, it is possible to form a film of a metal which is more electrochemically noble than nickel (in other words, a metal having a smaller ionization tendency) than the nickel.
  • the thickness of a film can be suitably adjusted with the processing time etc. of a substitution blackening treatment method. As a result, the film 18 can be disposed on the side surface portion 14 a of the underlayer 14.
  • FIG. 4 shows a partial cross-sectional view of a second embodiment of the conductive film of the present invention. Note that FIG. 4 corresponds to a cross-sectional view taken along the line BB in FIG. 2C.
  • the fine metal wires 32 in the conductive film 40 have a base layer 34 and a conductive layer 36 disposed in this order from the substrate 10 side, and a film 38 for covering the side surface portion 34 a of the base layer 34; including.
  • the conductive layer 36 is disposed on the surface 34b formed of the base layer 34 and the film 38 covering the side surface portion 34a of the base layer 34. That is, in the metal thin wire 32, the film 38 is not disposed so as to cover the periphery of the underlayer 34 and the conductive layer 36, and the film 38 is disposed only on the side surface portion 34a of the underlayer 34.
  • the line width L4 is 2.0 ⁇ m or less.
  • the thickness L5 of the film 38 is less than 100 nm. The measurement method of the line width L4 and the thickness L5 is measured by the same method as the line width L2 and the thickness L3, respectively.
  • Method of producing conductive film The manufacturing method in particular of the electroconductive film mentioned above is not restrict
  • a step of forming a base film on at least one of the main surfaces of a substrate (2) Step of forming a second metal film on the above-mentioned base film (second metal film forming step) (3) A step of forming a resist film having an opening in a region where a metal fine wire is formed on the second metal film (resist film formation step) (4) Step of forming a first metal film on the second metal film in the opening by plating (first metal film forming step) (5) Step of removing resist film (resist film removing step) (6) A step of removing a part of the second metal film and the base film by using the first metal film as a mask (a step of removing the second metal film and the base film) (7) Process of forming a film by substitution blackening treatment (film forming process)
  • the procedure of each of the above steps will be described in detail with reference to FIGS. 5A to 5G.
  • the base film forming step is a step of forming a base film on at least one main surface of the substrate. Specifically, as shown in FIG. 5A, the base film 44 is formed on the substrate 10 by performing this process. As described later, the base film 44 becomes the base layer 14 shown in FIG. 3 after predetermined processing.
  • the method for forming the underlayer 44 is not particularly limited, and any known method can be used. Among them, the sputtering method or the vapor deposition method is preferable in that a layer having a more dense structure can be easily formed.
  • the substrate 10 is as described above.
  • the base film 44 is a film to be the base layer 14 and is a film mainly composed of nickel.
  • the definition of the main component is as described for the base layer 14.
  • the second metal film forming step is a step of forming a second metal film on the base film. Specifically, as shown in FIG. 5B, the second metal film 46a is formed on the base film 44 by performing this process. As described later, the second metal film 46a functions as a seed layer in the plating method. As the metal contained in the second metal film 46a, a conductive layer having a predetermined composition may be formed, and examples thereof include the metals contained in the above-described seed layer.
  • the method of forming the second metal film 46a is not particularly limited, and any known method may be used, among which sputtering, vapor deposition, or electroless plating is preferable in that it is easy to form a layer having a more dense structure. The method is preferred.
  • the resist film forming step is a step of forming a resist film having an opening in a region where a metal thin wire is to be formed. Specifically, as shown in FIG. 5C, by performing this process, a resist film 47 is formed on the second metal film 46a.
  • the resist film 47 has an opening 49 in the region where the metal thin wire is to be formed.
  • the region of the opening 49 in the resist film 47 can be appropriately adjusted in accordance with the region in which the thin metal wire is to be disposed.
  • a resist film having openings in a mesh is formed in the case of forming metal thin wires arranged in a mesh.
  • the opening is formed in a thin wire shape in accordance with the thin metal wire.
  • the line width W of the opening is 2.0 ⁇ m or less.
  • the line width W is preferably 1.5 ⁇ m or less, and more preferably 1.2 ⁇ m or less. By setting the line width W of the opening to 2.0 ⁇ m or less, thin metal wires having a line width can be obtained.
  • the line width W of the opening when the line width W of the opening is 1.2 ⁇ m or less, the line width of the obtained metal thin line becomes narrower, and when the conductive film is applied to a touch panel sensor, for example, the metal thin line It is hard to see.
  • the lower limit of the line width W of the opening is not particularly limited, but is often 0.2 ⁇ m or more.
  • the width of the opening means the size of the thin line portion in the direction orthogonal to the extending direction of the thin line portion of the opening. Through each process described later, fine metal wires having a line width corresponding to the line width of the opening are formed.
  • the method of forming the resist film 47 on the second metal film 46a is not particularly limited, and a known resist film forming method can be used. For example, there is a method including the following steps.
  • C developing the resist film-forming composition after exposure to obtain a resist film.
  • the composition layer for resist film formation and / or a resist film are heated. The process may be further included.
  • Step (a) It does not restrict
  • a well-known composition for resist film formation can be used.
  • a composition for resist film formation a positive or negative radiation sensitive composition is mentioned, for example.
  • the composition layer for forming a resist film may be heated. By heating, the unnecessary solvent remaining in the composition layer for forming a resist film is removed, and the composition layer for forming a resist film can be made uniform in the plane.
  • limit especially as a method to heat the composition layer for resist film formation, For example, the method to heat a board
  • the temperature of the heating is not particularly limited, but generally 40 to 160 ° C. is preferable.
  • the thickness of the composition layer for forming a resist film is not particularly limited, but in general, the thickness after drying is preferably 0.5 to 2.5 ⁇ m.
  • Step (b) It does not restrict
  • a method of exposing the composition layer for forming a resist film for example, a method of irradiating the composition layer for forming a resist film with an actinic ray or radiation through a photomask provided with a pattern-like opening can be mentioned.
  • the exposure dose is not particularly limited, but in general, irradiation at 1 to 100 mW / cm 2 for 0.1 to 10 seconds is preferable.
  • the line width W of the pattern opening provided in the photomask used in the step (b) is generally preferably 2.0 ⁇ m or less, and 1.5 ⁇ m or less Is more preferable, and 1.2 ⁇ m or less is more preferable.
  • the composition layer for forming a resist film after exposure may be heated.
  • the heating temperature is not particularly limited, but generally 40 to 160 ° C. is preferable.
  • Step (c) It does not restrict
  • known development methods include methods using a developer containing an organic solvent or an alkali developer.
  • the development method include a dip method, a paddle method, a spray method, and a dynamic dispensing method.
  • the resist film after development may be washed using a rinse solution.
  • the rinse solution is not particularly limited, and known rinse solutions can be used. Examples of the rinse solution include organic solvents and water.
  • the first metal forming step is a step of forming the first metal film on the second metal film by the plating method in the opening of the resist film. Specifically, as shown in FIG. 5D, by performing this process, the first metal film 46b is formed on the second metal film 46a so as to fill the opening 49 in FIG. 5C.
  • the first metal film 46 b is formed by plating.
  • a well-known plating method can be used as a plating method. Specifically, electrolytic plating and electroless plating may be mentioned, and electrolytic plating is preferred from the viewpoint of productivity.
  • a metal contained in the first metal film 46b a conductive layer having a predetermined composition may be formed, and examples thereof include the metals contained in the above-described plating layer.
  • the resist film removing step is a step of removing the resist film 47. Specifically, as shown in FIG. 5E, by carrying out the present step, a stack including the substrate 10 and the base film 44, the second metal film 46a, and the first metal film 46b on the substrate 10 is provided. Get the body.
  • the method for removing the resist film 47 is not particularly limited, and a known method for removing the resist film 47 using a resist film removing solution may be mentioned.
  • Examples of the resist film removing solution include organic solvents and alkaline solutions.
  • the method for contacting the resist film removing solution with the resist film is not particularly limited, and examples thereof include a dip method, a paddle method, a spray method, and a dynamic dispensing method.
  • the second metal film and the underlayer film removing step is a step of removing a part of the second metal film and the underlayer film using the first metal film as a mask. Specifically, as shown in FIG. 5F, by performing this process, the base film 44 and the second metal film 46a corresponding to the area where the first metal film 46b is not formed are removed.
  • etching solution there is no particular limitation on the method of removing a part of the base film 44 and the second metal film 46a, but a known etching solution can be used.
  • known etching solutions include ferric chloride solution, cupric chloride solution, alkaline ammonia solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution.
  • an etching solution which does not easily dissolve the first metal film 46 b and easily dissolves the base film 44 and the second metal film 46 a may be selected appropriately.
  • the etching solution may be changed for each layer of the base film 44 and the second metal film 46a to perform multi-step etching.
  • the film forming step is a step of forming a film in a region including at least the side surface portion of the base film by substitution blackening treatment. Specifically, by carrying out this step, a region including at least the side surface portion of the base film 44 (in the method of manufacturing the conductive film 20, the base film 44, the second metal film 46a, and the first metal film 46b) Side surface portion is blackened, and as shown in FIG. 5G, on the substrate 10, the base layer 14, the conductive layer 16 including the second metal film 46a and the first metal film 46b, and the base layer A coating 18 covering the periphery of the conductive layer 14 and the conductive layer 16 is formed.
  • the conductive layer 16 and the film 18 in FIG. 5G correspond to the conductive layer 16 and the film 18 in FIG. 3, respectively. That is, the thin metal wires 12 shown in FIG. 3 are obtained through the film forming step.
  • the substitutional blackening treatment is a reaction utilizing the difference in ionization tendency among metals.
  • nickel on the side portion of the underlayer can be replaced with a metal that is more electrochemically noble than nickel (in other words, a metal having a smaller ionization tendency).
  • the substitutional blackening treatment method the above-mentioned laminate obtained through the second metal film and the base film removing step is immersed in an aqueous solution containing metal ions having a smaller ionization tendency than nickel.
  • the nickel constituting the layer is dissolved to form nickel ions to emit electrons.
  • the electrons reduce a metal having a small ionization tendency contained in the aqueous solution, whereby a metal having a small ionization tendency is deposited on the side portion of the base film 44.
  • the film 18 can be disposed on the side surface of the base layer 14.
  • the nickel contained in the base layer 14 is mainly contained in the first metal film 46b.
  • the metal as the main component of the first metal film 46 b and the metal as the main component of the second metal film 46 a are preferably both copper, and in this case, as the metal ion, it is preferable to use silver. Also, metal ions having a smaller ionization tendency are preferable, and palladium ions are more preferable.
  • the liquid temperature of the solution at the time of immersion is not particularly limited, but usually 10 to 90 ° C., preferably 20 to 60 ° C.
  • the pH of the solution at the time of immersion is not particularly limited, but it is preferably 0 to 13, and more preferably 0 to 8.
  • the immersion time is not particularly limited, but is usually 1 to 8 minutes.
  • substitution blackening treatment method is not restrict
  • the composition for blackening treatment described in patent publication 586 2916 can be used.
  • the conductive film 20 can be formed through the above steps.
  • the conductive film 40 shown in FIG. 4 can also be manufactured by the same method.
  • a coating is not formed around the conductive layer 36 as in the thin metal wire 32 shown in FIG. 4 and only the side surface portion 34 a of the base layer 34 is covered with the coating 38, the ionization tendency is lower in the coating forming step.
  • the metal as the main component of the first metal film 46b and the metal as the main component of the second metal film 46a are both copper, and in this case, tin, as the metal ion, is used. Lead, antimony, bismuth and the like can be mentioned.
  • the conductive film of the present invention can be used in various applications.
  • various electrode films, heat generating sheets, and printed wiring boards can be mentioned.
  • the conductive film is preferably used for a touch panel sensor, and more preferably used for a capacitive touch panel sensor.
  • the touch panel including the conductive film as a touch panel sensor it is difficult for a thin metal wire to be visible.
  • Examples of the configuration of the touch panel include the touch panel module described in paragraphs 0020 to 0027 of JP-A-2015-195004, and the above contents are incorporated in the present specification.
  • Example 1 On a PET (polyethylene terephthalate) film, a Ni film having a thickness of 20 nm was formed as a base film using a sputtering apparatus. Next, using a sputtering apparatus, a Cu film (second metal film) having a thickness of 50 nm was formed as a seed film on the Ni film. Next, on the second metal film, a positive resist (MCP R 124 MG manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied by a spin coater so as to have a thickness of 1 ⁇ m, and dried at 90 ° C. for 10 minutes.
  • MCP R 124 MG manufactured by Rohm and Haas Electronic Materials Co., Ltd.
  • the resist film After irradiating a light of 365 nm wavelength (exposure amount: 16 mw / cm 2 ) for 2 seconds using a parallel exposure machine through a photomask, the resist film is developed by developing with a 0.10 M sodium hydroxide aqueous solution. Obtained (line width of the opening of the resist film: 1.5 ⁇ m ⁇ 0.1 ⁇ m). Next, the entire surface of the resist was exposed (3 seconds at an exposure amount of 16 mW / cm 2 ) for later peeling.
  • electroplating is performed at a current density of 3 A / dm 2 using a copper sulfate high-throw bath (including Top Lucina HT-A and Top Lucina HT-B as additives, each of which is manufactured by Okuno Pharmaceutical Industry Co., Ltd.)
  • the Cu plating film (1st metal film) formed so that a part was filled was obtained.
  • the resist was peeled off with a 0.15 M aqueous solution of sodium hydroxide, and then the second metal film in the opening was removed with a Cu etching solution (Cu etchant manufactured by Wako Pure Chemical Industries, Ltd.).
  • the underlayer was etched with a Ni etching solution (NC-A and NC-B manufactured by Nippon Chemical Industrial Co., Ltd.). Finally, a surface treatment is carried out with a Pd solution (example 1 of Patent No. 586 2916, prepared with reference to blackening solution No. 2) at room temperature for 3 minutes to form a film (Pd layer), whereby the conductivity is achieved. A film was obtained (line width of 1 ⁇ m ⁇ 0.1 ⁇ m of fine metal wire). The thickness of the film (corresponding to L3 in FIG. 3) in this example was 40 nm.
  • the metal thin wires formed on the substrate are the base layer and the conductive layer disposed in this order from the substrate side, and the periphery of the base layer and the conductive layer. And a coating to be coated.
  • the conductive layer contains copper as a main component (the content of copper is specifically 90% by mass or more with respect to the entire conductive layer).
  • the conductive layer is composed of the first metal film and the second metal film.
  • the underlayer is made of Ni alone. Also, the film contains palladium.
  • the line width of the thin metal wire in the produced conductive film was measured by the following method. First, the above conductive film is embedded in a resin together with the substrate, cut with an ultramicrotome in the width direction (direction orthogonal to the extending direction of the metal fine wire), and carbon is deposited on the obtained cross section , And was observed using a scanning electron microscope (S-5500 manufactured by Hitachi High-Technologies Corporation). When the line width differs in the height direction, the largest measurement width is defined as the line width.
  • the thickness of the film of the metal fine wire in the produced conductive film was measured by the following method. First, C deposition and Pt coating were performed on the conductive part of the conductive film for conductivity imparting and surface protection. Subsequently, the metal thin wire was cut in the width direction (direction orthogonal to the extending direction of the metal thin wire) using a Helios 400 type FIB-SEM (FIB: Focused Ion Beam, SEM: Scanning Electron Microscope) composite machine manufactured by FEI. Then, using the obtained section, EDS analysis was performed at an acceleration voltage of 200 kV with an EDS detector (HD2300 type FE-STEM manufactured by Hitachi High-Technologies Corporation). In element mapping obtained by EDS analysis, the thickness of the distribution region of Pd atoms was measured one by one for each of the films disposed at both ends of the section, and the average value was taken as the thickness of the film.
  • FIB-SEM Focused Ion Beam
  • SEM Scanning Electro
  • the obtained conductive film was exposed to 85 ° C. and 85% Rh conditions for 168 hours.
  • the tape adhesion test shown below was implemented with respect to the conductive film after exposing to the conditions of 85 degreeC 85% Rh for 168 hours. As a result, peeling of the thin metal wires arranged in a mesh was not seen.
  • the adhesion of the metal thin line to the substrate was evaluated by a tape adhesion test.
  • a cellophane tape film ("CT24" manufactured by Nichiban Co., Ltd.) is pressed against the main surface of the substrate provided with metal fine wires using a conductive film produced by the above method and then adhered with a finger pad, and then cellophane tape Peeled off. Thereafter, the peeled area (%) of the metal thin wire on the substrate (area of peeled metal thin wire / area of metal thin wire in test piece ⁇ 100) was visually confirmed.
  • Example 2 The procedure was carried out in the same manner as in Example 1 except that a COP (cycloolefin polymer) film was used as a substrate. That is, the second embodiment is different from the first embodiment only in the type of the substrate. Moreover, the tape adhesion test was implemented with respect to the electroconductive film after 168 hours of exposure conditions of 85 degreeC 85% Rh similarly to Example 1. FIG. As a result, peeling of the thin metal wires arranged in a mesh was not seen. The thickness of the film (corresponding to L3 in FIG. 3) in this example was 40 nm.
  • Example 3 Everything was carried out in the same manner as in Example 1 except that the surface treatment was carried out for 5 minutes. In other words, Example 3 is different from Example 1 only in the thickness of the film. Moreover, the tape adhesion test was implemented with respect to the electroconductive film after 168 hours of exposure conditions of 85 degreeC 85% Rh similarly to Example 1. FIG. As a result, peeling of the thin metal wires arranged in a mesh was not seen. The thickness of the film (corresponding to L3 in FIG. 3) in this example was 80 nm.
  • Example 4 The second metal film was performed in the same manner as in Example 1 except that a Cu—Zn alloy film (component ratio 85: 15 (mass ratio) of a sputtering target) was used instead of the Cu film.
  • a Cu—Zn alloy film component ratio 85: 15 (mass ratio) of a sputtering target
  • the fourth embodiment is different from the first embodiment only in the type of the second metal film.
  • the conductive layer contains copper as a main component (the content of copper is specifically 90% by mass or more with respect to the entire conductive layer). is there).
  • the conductive layer is composed of the first metal film and the second metal film.
  • the tape adhesion test was implemented with respect to the electroconductive film after exposing to the conditions of 85 degreeC 85% Rh for 168 hours similarly to Example 1.
  • FIG. As a result, peeling of the thin metal wires arranged in a mesh was not seen.
  • the thickness of the film (corresponding to L3 in FIG. 3) in this example was 40 nm.
  • Example 5 The procedure was carried out in the same manner as in Example 4 except that a COP film was used as a substrate. That is, the fifth embodiment is different from the fourth embodiment only in the type of the substrate. Moreover, the tape adhesion test was implemented with respect to the electroconductive film after exposing to the conditions of 85 degreeC 85% Rh for 168 hours similarly to Example 1. FIG. As a result, peeling of the thin metal wires arranged in a mesh was not seen. The thickness of the film (corresponding to L3 in FIG. 3) in this example was 40 nm.
  • Comparative Example 1 It carried out like Example 1 except not having implemented surface treatment by Pd solution. That is, the conductive film of the comparative example 1 is a structure which does not have a film. Moreover, the tape adhesion test was implemented with respect to the electroconductive film after exposing to the conditions of 85 degreeC 85% Rh for 168 hours similarly to Example 1. FIG. As a result, 50% or more of the metal thin wires arranged in a mesh were peeled off.
  • Comparative Example 2 Everything was carried out in the same manner as in Example 1 except that the surface treatment was carried out for 10 minutes. That is, the conductive film of Comparative Example 1 has the same configuration as the conductive film of Example 1 except that the thickness of the film is 100 nm.
  • the above-mentioned tape adhesion test was conducted, and peeling was observed in an area range of 3% or less of the metal thin wires arranged in a mesh shape.
  • the tape adhesion test was implemented with respect to the electroconductive film after 168 hours of exposure to 85 degreeC 85% Rh conditions similarly to Example 1, it arrange
  • the thickness of the film (corresponding to L3 in FIG. 3) in this example was 100 nm.
  • the conductive film of the example had excellent adhesion to the substrate over a long period of time while the line width was 2.0 ⁇ m or less.

Abstract

La présente invention a pour objet de fournir un film conducteur qui comprend un fil mince métallique qui a une largeur de ligne inférieure ou égale à 2,0 µm et qui présente une excellente adhérence à un substrat pendant une longue durée de temps. La présente invention a également pour objet de fournir un capteur de panneau tactile et un panneau tactile, comprenant chacun ledit film conducteur. Un film conducteur selon la présente invention comprend un substrat et une partie conductrice qui est disposée sur au moins une surface principale du substrat et est composée d'un fil mince métallique. Le fil mince métallique comprend une couche de base et une couche conductrice, qui sont agencées de manière séquentielle dans cet ordre à partir du côté substrat, et un film de revêtement qui recouvre une partie de surface latérale de la couche de base ; et le fil mince métallique a une largeur de ligne inférieur ou égale à 2,0 µm. La couche de base contient du nickel élémentaire en tant que composant principal ; la couche conductrice contient du cuivre en tant que composant principal ; et le film de revêtement a une épaisseur inférieure à 100 nm et contient un métal qui est sélectionné parmi les métaux qui sont électrochimiquement plus nobles que le nickel.
PCT/JP2018/030305 2017-09-05 2018-08-14 Film conducteur, capteur de panneau tactile et panneau tactile WO2019049617A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017170398 2017-09-05
JP2017-170398 2017-09-05

Publications (1)

Publication Number Publication Date
WO2019049617A1 true WO2019049617A1 (fr) 2019-03-14

Family

ID=65634009

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/030305 WO2019049617A1 (fr) 2017-09-05 2018-08-14 Film conducteur, capteur de panneau tactile et panneau tactile

Country Status (1)

Country Link
WO (1) WO2019049617A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014089689A (ja) * 2012-10-29 2014-05-15 Samsung Electro-Mechanics Co Ltd タッチパネル及びその製造方法
JP5862916B1 (ja) * 2014-06-24 2016-02-16 奥野製薬工業株式会社 銅系金属又は銀系金属の黒化処理用組成物
JP2016540304A (ja) * 2013-12-13 2016-12-22 エルジー・ケム・リミテッド タッチセンサおよびその製造方法｛ｔｏｕｃｈ ｓｅｎｓｏｒ ａｎｄ ｍｅｔｈｏｄ ｆｏｒ ｍａｎｕｆａｃｔｕｒｉｎｇ ｓａｍｅ｝
JP2017027446A (ja) * 2015-07-24 2017-02-02 住友金属鉱山株式会社 導電性基板、導電性基板の製造方法
JP2017059171A (ja) * 2015-09-18 2017-03-23 日立化成株式会社 静電容量方式タッチパネル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014089689A (ja) * 2012-10-29 2014-05-15 Samsung Electro-Mechanics Co Ltd タッチパネル及びその製造方法
JP2016540304A (ja) * 2013-12-13 2016-12-22 エルジー・ケム・リミテッド タッチセンサおよびその製造方法｛ｔｏｕｃｈ ｓｅｎｓｏｒ ａｎｄ ｍｅｔｈｏｄ ｆｏｒ ｍａｎｕｆａｃｔｕｒｉｎｇ ｓａｍｅ｝
JP5862916B1 (ja) * 2014-06-24 2016-02-16 奥野製薬工業株式会社 銅系金属又は銀系金属の黒化処理用組成物
JP2017027446A (ja) * 2015-07-24 2017-02-02 住友金属鉱山株式会社 導電性基板、導電性基板の製造方法
JP2017059171A (ja) * 2015-09-18 2017-03-23 日立化成株式会社 静電容量方式タッチパネル

Similar Documents

Publication Publication Date Title
WO1999034658A1 (fr) Element transparent de blindage contre des ondes electromagnetiques et son procede de production
WO2018221183A1 (fr) Procédé de fabrication d'un substrat électroconducteur transparent, et substrat électroconducteur transparent
US20190333656A1 (en) Method of manufacturing conductive film and conductive film
JP2020074114A (ja) 導電性フィルム、タッチパネルセンサー、および、タッチパネル
WO2019065782A1 (fr) Film conducteur, capteur de panneau tactile, panneau tactile et procédé de production de film conducteur
JP3502979B2 (ja) 電磁波シールド用透明部材とその製造方法
WO2019049617A1 (fr) Film conducteur, capteur de panneau tactile et panneau tactile
WO2018047608A1 (fr) Procédé de production de film conducteur, film conducteur, capteur de panneau tactile, antenne, authentification d'empreintes digitales, et panneau tactile
JP7031663B2 (ja) 導電性基板
JP6722291B2 (ja) 導電性フィルム、タッチパネル、フォトマスク、インプリントテンプレート、導電性フィルム形成用積層体、導電性フィルムの製造方法、および電子デバイスの製造方法
JPWO2017130865A1 (ja) 黒化めっき液、導電性基板の製造方法
JPWO2017022596A1 (ja) 導電性基板、導電性基板の製造方法
WO2018042979A1 (fr) Procédé pour fabriquer un film conducteur, film conducteur, capteur de panneau tactile et panneau tactile
JP6432684B2 (ja) 導電性基板、導電性基板の製造方法
JP6791172B2 (ja) 導電性基板
JP6365422B2 (ja) 導電性基板の製造方法
JPWO2017130869A1 (ja) 黒化めっき液、導電性基板の製造方法
JP6848243B2 (ja) 導電性基板の製造方法
JPWO2017022543A1 (ja) 導電性基板、導電性基板の製造方法
JP6439628B2 (ja) 導電性基板の製造方法
JP2009054670A (ja) 光透過性電磁波シールド部材およびその製造方法、ならびにそれを用いたフィルターおよびディスプレイ
JPWO2017130866A1 (ja) 黒化めっき液、導電性基板の製造方法
JP2017182271A (ja) 導電性フィルム、導電性フィルムの製造方法、タッチパネル、電子デバイス、透明アンテナおよび窓ガラス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18854311

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18854311

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP