WO2017183489A1 - Substrat conducteur et procede de fabrication d'un substrat conducteur - Google Patents

Substrat conducteur et procede de fabrication d'un substrat conducteur Download PDF

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Publication number
WO2017183489A1
WO2017183489A1 PCT/JP2017/014575 JP2017014575W WO2017183489A1 WO 2017183489 A1 WO2017183489 A1 WO 2017183489A1 JP 2017014575 W JP2017014575 W JP 2017014575W WO 2017183489 A1 WO2017183489 A1 WO 2017183489A1
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WIPO (PCT)
Prior art keywords
layer
copper
substrate
metal
wiring
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Application number
PCT/JP2017/014575
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English (en)
Japanese (ja)
Inventor
下地　匠
Original Assignee
住友金属鉱山株式会社
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Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201780014220.1A priority Critical patent/CN108700969B/zh
Priority to JP2018513115A priority patent/JP7101113B2/ja
Publication of WO2017183489A1 publication Critical patent/WO2017183489A1/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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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 conductive substrate and a method for manufacturing a conductive substrate.
  • the capacitive touch panel converts information on the position of an adjacent object on the panel surface into an electrical signal by detecting a change in capacitance caused by the object adjacent to the panel surface. Since the conductive substrate used for the capacitive touch panel is installed on the surface of the display, the material of the conductive layer of the conductive substrate is required to have low reflectance and be difficult to be visually recognized.
  • a material for the conductive layer used for the capacitive touch panel a material having low reflectivity and not easily visible is used, and wiring is formed on a transparent substrate or a transparent film.
  • Patent Document 1 discloses a transparent conductive film including a polymer film and a transparent conductive film made of a metal oxide provided thereon by a vapor deposition method, and the transparent conductive film made of a metal oxide. Is made of a transparent conductive film made of the first metal oxide and a transparent conductive film made of the second metal oxide provided thereon, and the transparent conductive film made of the second metal oxide is the first A transparent conductive film characterized by being formed under conditions different from the film forming conditions of a transparent conductive film made of a metal oxide is disclosed. It is also disclosed that the transparent conductive film made of a metal oxide is an indium oxide-tin oxide (ITO) film.
  • ITO indium oxide-tin oxide
  • a display equipped with a touch panel has been increased in screen size and performance, and in order to cope with this, a metal such as copper is used instead of ITO having a high electrical resistance as a material of the conductive layer.
  • a metal such as copper is used instead of ITO having a high electrical resistance as a material of the conductive layer.
  • the metal has a metallic luster, there is a problem that the visibility of the display decreases due to reflection. For this reason, a conductive substrate having a blackened layer made of a black material together with a metal layer such as copper serving as a conductive layer has been studied.
  • the metal wiring constituting the wiring pattern as described above has a metal layer such as copper and a blackened layer
  • a metal layer and a blackened layer are previously formed on a base material. It is necessary to produce a laminated substrate and to etch the metal layer and the blackened layer according to the pattern of the metal wiring.
  • the reactivity of the metal layer such as copper and the blackened layer with respect to the etching solution is different, and the blackened layer cannot be completely removed, and the blackened layer residue remains in the opening between the metal wirings.
  • the visible light transmittance of the transparent base material exposed to the part was low.
  • an object of one aspect of the present invention is to provide a conductive substrate having a high visible light transmittance of a transparent base material exposed between metal wirings.
  • a transparent substrate Metal wiring formed on at least one surface of the transparent substrate, The metal wiring has a structure in which a copper wiring layer and a blackened wiring layer containing nickel and copper are laminated, The transparent substrate exposed from between the metal wirings provides a conductive substrate having a visible light transmittance of 90% or more and b * of 1.0 or less.
  • a conductive substrate having a high visible light transmittance of a transparent base material exposed between metal wirings can be provided.
  • substrate which concerns on embodiment of this invention Sectional drawing of the laminated body board
  • Sectional drawing in the AA 'line of FIG. Sectional drawing in the AA 'line of FIG. Explanatory drawing of an etching process.
  • the conductive substrate of this embodiment can have a transparent base material and metal wiring formed on at least one surface of the transparent base material.
  • the metal wiring has a structure in which a copper wiring layer and a blackened wiring layer containing nickel and copper are laminated, and the transparent substrate exposed from between the metal wiring has a visible light transmittance of 90%. It is above and b * can be 1.0 or less.
  • substrate in this embodiment means the board
  • the conductive substrate means a substrate obtained by patterning a copper layer and a blackened layer so as to have a desired wiring pattern, that is, a wiring substrate. Since the conductive substrate includes a region where the transparent base material is not covered with a copper layer or the like, the conductive substrate can transmit light and is a transparent conductive substrate.
  • the conductive substrate of this embodiment has a transparent substrate and a metal laminate formed on at least one surface of the transparent substrate, and the metal laminate contains a copper layer, nickel and copper. It can be produced by patterning the copper layer and the blackened layer of the laminate substrate having a structure in which the blackened layer to be laminated is laminated. For this reason, the structural example of the laminated body board
  • the transparent substrate is not particularly limited, and an insulating film that transmits visible light, a glass substrate, or the like can be preferably used.
  • the insulator film that transmits visible light examples include one or more resin films selected from polyamide film, polyethylene terephthalate film, polyethylene naphthalate film, cycloolefin film, polyimide film, polycarbonate film, and the like. Etc. can be preferably used.
  • a material for an insulating film that transmits visible light one or more selected from PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyimide, polyamide, polycarbonate, and the like are more preferable. Can be used.
  • the thickness of the transparent base material is not particularly limited, and can be arbitrarily selected according to the strength required when a conductive substrate is used, the capacitance, the light transmittance, and the like.
  • the thickness of the transparent substrate can be, for example, 10 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the transparent substrate is preferably 20 ⁇ m or more and 120 ⁇ m or less, and more preferably 20 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the transparent substrate is preferably 20 ⁇ m or more and 50 ⁇ m or less.
  • the transparent substrate preferably has a higher visible light transmittance, for example, the visible light transmittance is preferably 90% or more. This can sufficiently ensure the visibility of the display when the transparent substrate has a visible light transmittance of 90% or more, for example, when used for a touch panel.
  • the visible light transmittance of the transparent substrate can be evaluated by the method specified in JIS K 7361-1.
  • the metal laminate can have a structure in which a copper layer and a blackening layer containing nickel and copper are laminated.
  • the copper layer can be composed of copper. However, the inevitable component mixed in the manufacturing process resulting from a target, a plating solution, etc. may be included.
  • the method for forming the copper layer is not particularly limited, but is preferably formed without disposing an adhesive between the other member and the copper layer in order not to reduce the light transmittance. That is, the copper layer is preferably formed directly on the upper surface of another member.
  • the copper layer can be formed on the blackened layer or the upper surface of the transparent substrate. For this reason, it is preferable that the copper layer is directly formed on the blackened layer or the upper surface of the transparent substrate.
  • the copper layer preferably has a copper thin film layer formed by using a dry plating method.
  • a dry-type plating method For example, a vapor deposition method, sputtering method, an ion plating method etc. can be used.
  • the sputtering method is preferably used because the film thickness can be easily controlled.
  • the copper plating layer can be laminated on the copper thin film layer by using a wet plating method after the dry plating.
  • a copper thin film layer is formed on a transparent substrate or a blackened layer by a dry plating method, and the copper thin film layer is used as a power feeding layer, and copper plating is performed by an electrolytic plating method which is a kind of wet plating method.
  • a layer can be formed.
  • the copper layer can be constituted by a copper thin film layer.
  • the copper layer can be composed of a copper thin film layer and a copper plating layer.
  • Forming a copper layer directly on a transparent substrate or blackened layer without using an adhesive by forming a copper layer only by dry plating as described above, or by combining dry plating and wet plating. Can do.
  • the thickness of the copper layer is not particularly limited, and when the copper layer is patterned to form a copper wiring layer, it can be arbitrarily selected according to the magnitude of current supplied to the copper wiring layer, the wiring width, etc. Can do.
  • the thickness of a copper layer is 5 micrometers or less, and it is more preferable that it is 1 micrometer or less.
  • the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and 150 nm. More preferably, it is the above.
  • a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.
  • the thickness of the copper thin film layer is not particularly limited in either case where the copper layer is constituted by a copper thin film layer or in the case where the copper thin film layer and the copper plating layer are constituted, for example, 50 nm
  • the thickness is preferably 500 nm or more.
  • the wiring Since the copper layer has a metallic luster, the wiring reflects light only by forming a metal wiring layer by etching the copper layer on a transparent substrate. For example, when used as a wiring board for a touch panel, the visibility of the display There was a problem that decreased. Therefore, a method of providing a blackened wiring layer on the surface of the metal wiring layer on which light reflection is to be suppressed has been studied.
  • the blackened layer cannot be completely removed, and the blackened layer residue may remain in the opening between the metal wirings. There is a problem that the visible light transmittance of the transparent base material exposed to the portion is lowered.
  • the inventor of the present invention uses the blackening layer as a layer containing nickel and copper and uses a predetermined etching solution, so that the transparent substrate exposed to the opening between the metal wirings has high visible light transmittance.
  • the inventors have found that a conductive substrate can be obtained and completed the present invention.
  • the blackened layer of the conductive substrate of this embodiment can contain nickel and copper, and can also contain, for example, oxygen.
  • the blackening layer of the conductive substrate of this embodiment can also be composed of nickel, copper and oxygen.
  • the blackening layer contains nickel and copper, so that reflection of light on the surface of the copper layer can be sufficiently suppressed, and even when the copper layer and the blackening layer are patterned, it is transparent. It can suppress that the residue of a blackening layer arises on the base-material surface.
  • the method for forming the blackened layer is not particularly limited, and any method can be selected as long as it can be formed so as to contain nickel and copper.
  • the blackening layer is preferably formed directly on the upper surface of another member such as a transparent substrate and / or a copper layer without using an adhesive.
  • a method for forming the blackened layer for example, a wet plating method or a dry plating method can be used.
  • the wet plating method for example, an electrolytic plating method can be used.
  • the dry plating method for example, an evaporation method, a sputtering method, an ion plating method, or the like can be used.
  • the plurality of blackening layers included in the same laminate substrate may be formed by the same film formation method or by different film formation methods.
  • a film may be formed.
  • the thickness of the blackening layer is not particularly limited, and can be arbitrarily selected depending on the degree of suppression of light reflection required for the laminate substrate or the conductive substrate.
  • the thickness of the blackening layer is preferably 15 nm or more, for example, and more preferably 20 nm or more.
  • the blackened layer has a function of suppressing light reflection by the copper layer, but when the thickness of the blackened layer is thin, reflection of light by the copper layer may not be sufficiently suppressed. On the other hand, it is preferable to set the thickness of the blackened layer to 15 nm or more because reflection on the surface of the copper layer can be more reliably suppressed.
  • the upper limit of the thickness of the blackening layer is not particularly limited, but if it is thicker than necessary, the time required for etching when forming the metal wiring becomes longer, leading to an increase in cost. .
  • the thickness of the blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.
  • the laminate substrate of this embodiment can have a transparent base material, a copper layer, and a blackened layer.
  • stacking on a transparent base material about a copper layer and a blackening layer is not specifically limited. Further, a plurality of copper layers and blackening layers can be formed. However, in order to suppress the reflection of light on the surface of the copper layer, it is preferable to dispose a blackening layer on the surface of the copper layer on which the reflection of light is particularly desired to be suppressed.
  • a laminated structure in which the blackened layer is formed on the upper and lower surfaces of the copper layer that is, a structure in which the copper layer is sandwiched between the blackened layers. You can also.
  • FIG. 1 and FIG. 2 show examples of cross-sectional views in a plane parallel to the lamination direction of the transparent base material, the copper layer, and the blackening layer of the laminate substrate of the present embodiment.
  • the laminate substrate of the present embodiment can have a structure in which, for example, a copper layer and a blackening layer are laminated on at least one surface of a transparent substrate.
  • the copper layer 12 and the blackening layer 13 may be laminated one layer at a time on the one surface 11a side of the transparent base material 11. it can.
  • the copper layer 12 and the blackened layer 13 constitute a metal laminate 14.
  • copper layers 12A and 12B and black layers are formed on one surface 11a side of the transparent base material 11 and the other surface 11b side, which is the other surface, respectively.
  • the layers 13A and 13B can be stacked one by one in that order.
  • the copper layer 12A and the blackened layer 13A have the metal laminate 14A on the one surface 11a side
  • the copper layer 12B and the blackened layer 13B have the metal laminate 14B on the other surface 11b side. It is composed.
  • the order in which the copper layer 12 (12A, 12B) and the blackening layer 13 (13A, 13B) are stacked is not limited to the example of FIGS. 1A and 1B, and the blackening layer 13 is formed from the transparent substrate 11 side. (13A, 13B) and copper layer 12 (12A, 12B) may be laminated in this order.
  • a configuration in which a plurality of blackening layers are provided on one surface side of the transparent substrate 11 may be employed.
  • a structure in which a blackened layer, a copper layer, and a blackened layer are formed in this order on at least one surface of the transparent substrate from the transparent substrate side can be employed.
  • the first blackened layer 131, the copper layer 12, and the second blackened layer 132 are formed on one surface 11a side of the transparent base material 11. , Can be stacked in that order.
  • the first blackened layer 131, the copper layer 12, and the second blackened layer 132 constitute the metal laminate 24.
  • first blackened layer and the second blackened layer are also simply referred to as blackened layers when collectively shown without being distinguished from each other.
  • the first blackening layer 131A is formed on one surface 11a side and the other surface (the other surface) 11b side of the transparent base material 11, respectively.
  • 131B, copper layers 12A and 12B, and second blackening layers 132A and 132B can be stacked in that order.
  • the layers laminated on the upper and lower sides of the transparent substrate 11 are symmetrical with the transparent substrate 11 as a symmetry plane.
  • the configuration on the one surface 11a side of the transparent base material 11 is a form in which a copper layer 12 and a blackening layer 13 are laminated in that order, similarly to the configuration of FIG.
  • the layers stacked above and below may be asymmetrical.
  • the laminate substrate of the present embodiment has been described.
  • the copper layer and the blackened layer are provided on the transparent base material. Reflection can be suppressed.
  • the conductive substrate of this embodiment will be described below.
  • the conductive substrate of the present embodiment has a configuration in which the metal laminate of the laminate substrate described so far is patterned into a metal wiring having a predetermined wiring pattern.
  • the transparent base material, the copper wiring layer, and the blackened wiring layer which the conductive substrate of this embodiment has are respectively made of the same materials as the transparent base material, the copper layer, and the blackened layer described in the multilayer substrate. It can be used, and the suitable thickness of each member can be set in the same range. Therefore, description of points already described in the multilayer substrate is omitted.
  • FIG. 3 shows a configuration example of a cross-sectional view in a plane parallel to the stacking direction of each layer of the conductive substrate of the present embodiment.
  • the conductive substrate of the present embodiment includes a transparent base material 11 and a metal wiring 34 formed on at least one surface of the transparent base material 11.
  • a structure in which the copper wiring layer 32 and the blackened wiring layer 33 containing nickel and copper are stacked can be provided.
  • the conductive substrate 30 shown in FIG. 3 can be formed, for example, by patterning the metal laminate 14 of the laminate substrate 10A shown in FIG. 1A described above.
  • the metal wiring 34 has shown the example laminated
  • the blackened wiring layer 33 and the copper wiring layer 32 may be stacked in this order from the transparent substrate 11 side.
  • the conductive substrate of this embodiment can also be produced by patterning the metal laminate of the laminate substrate shown in FIGS. 1B, 2A, and 2B, for example.
  • the metal laminate 14A (24A) and the metal laminate 14B (24B) are patterned, and the conductive material having metal wiring on both surfaces of the transparent substrate 11 is used. It can be a substrate.
  • a conductive substrate having a metal wiring in which a copper wiring layer is disposed between blackened wiring layers can be obtained.
  • the conductive substrate of this embodiment preferably has a visible light transmittance of 90% or more of the transparent base material 11 exposed from between the metal wirings 34.
  • the transparent substrate 11 exposed from between the metal wirings 34 has a visible light transmittance of 90% or more, the surface of the transparent substrate at the opening between the metal wirings formed by patterning the metal laminate is blackened. This means that almost no layer residue remains.
  • the visible light transmittance of the transparent base material 11 exposed from between the metal wirings 34 is 90% or more, for example, when used as a conductive substrate for a touch panel, the visibility of the display can be particularly enhanced, preferable.
  • the visible light transmittance of the transparent base material exposed from between the metal wirings means, for example, the visible light transmittance of the transparent base material 11 exposed at the opening 35 between the metal wirings 34 in FIG.
  • the visible light transmittance of the transparent base material 11 exposed at the opening 35 between the metal wirings 34 in FIG. when producing a conductive substrate from a laminate substrate having a metal laminate on one side of the transparent base and both sides of the other side as shown in FIG. 1B and FIG. This means the visible light transmittance at a portion that is not covered with the metal wiring on both the one surface and the other surface.
  • the visible light transmittance is, for example, by irradiating light having a wavelength of 400 nm or more and 700 nm or less at a predetermined interval, specifically, for example, a 1 nm interval, and irradiating the transparent substrate exposed from between the metal wirings, It means the average value of transmittance measured for light of wavelength.
  • b * of the transparent base material 11 exposed from between the metal wirings 34 that is, the color of the transmitted light of the transparent base material 11 exposed from between the metal wirings 34 is CIE (L * a * b * )
  • the b * value when converted to the color system is preferably 1.0 or less.
  • b * of the transparent base material 11 exposed from between the metal wirings 34 is, for example, the transparent base material exposed at the opening 35 between the metal wirings 34 in FIG. 3 as in the case of the visible light transmittance described above. It means 11 b * .
  • the blackened layer is formed on the transparent base material surface of the opening between the metal wirings 34 formed by patterning the metal laminate. This means that almost no residue remains. And when b * in the opening part 35 between the metal wiring 34 is 1.0 or less, when using as a conductive substrate for touch panels, for example, the visibility of the display can be particularly improved, which is preferable.
  • the lower limit value of b * is not particularly limited, but can be, for example, 0.1 or more.
  • the b * of the transparent base material 11 exposed from between the metal wirings 34 can be measured in accordance with JIS Z 8722 (revised in 2009), for example, with respect to the transparent base material 11 exposed at the opening 35 between the metal wirings 34. .
  • the conductive substrate of this embodiment can be a conductive substrate provided with, for example, mesh-like metal wiring.
  • a conductive substrate having mesh-like metal wiring will be described below as an example.
  • mesh wiring can be formed by two-layer metal wiring.
  • FIG. FIG. 4 shows a view of the conductive substrate 40 having mesh-like wiring as viewed from the upper surface side in the stacking direction of the copper wiring layer and the blackened wiring layer.
  • the conductive substrate 40 shown in FIG. 4 includes the transparent substrate 11, a plurality of metal wirings 44A parallel to the Y-axis direction in the drawing, and metal wirings 44B parallel to the X-axis direction.
  • the metal wirings 44A and 44B have a copper wiring layer and a blackened wiring layer, and the copper wiring layer and the blackened wiring layer are parallel to the surface on which the metal wiring of the transparent substrate 11 is arranged. Etching is preferably performed so that the cross-section of the film has the same shape.
  • the arrangement of the transparent substrate 11 and the metal wirings 44A and 44B is not particularly limited.
  • positioning with the transparent base material 11 and metal wiring is shown to FIG. 5A and FIG. 5B.
  • 5A and 5B are cross-sectional views taken along the line AA ′ of FIG.
  • copper wiring layers 42A and 42B may be disposed on the upper and lower surfaces of the transparent substrate 11, respectively.
  • the cross section in the plane parallel to the surface on which the metal wiring of the transparent base material 11 is arranged has the same shape as the copper wiring layer.
  • the first blackened wiring layers 431A and 431B etched so as to be can be disposed.
  • the cross section of the surface of the transparent base material 11 parallel to the surface on which the metal wiring is arranged is a copper wiring layer.
  • Second blackened wiring layers 432A and 432B etched so as to have the same shape can be disposed.
  • a pair of transparent base materials 11A and 11B is used, and copper wiring layers 42A and 42B are arranged on the upper and lower surfaces with one transparent base material 11A interposed therebetween, and one copper wiring The layer 42B may be disposed between the transparent substrates 11A and 11B.
  • a cross section in a plane parallel to the surface on which the metal wirings of the transparent base materials 11A and 11B are arranged is between the copper wiring layers 42A and 42B and the transparent base materials 11A and 11B.
  • the first blackened wiring layers 431A and 431B etched so as to have the same shape as 42A and 42B can be disposed.
  • Second blackened wiring layers 432A and 432B etched to have the same shape as the copper wiring layers 42A and 42B can be disposed.
  • the metal wiring 44A is formed of the copper wiring layer 42A, the first blackened wiring layer 431A, and the second blackened wiring layer 432A, and the copper wiring layer 42B and the first blackened wiring layer 431B.
  • the second blackening wiring layer 432B constitutes the metal wiring 44B.
  • 5A and 5B show an example in which the first blackened wiring layers 431A and 431B and the second blackened wiring layers 432A and 432B are arranged.
  • the present invention is not limited to this mode. It can also be set as the structure which does not have any one blackening wiring layer.
  • the blackened wiring layer is preferably disposed on the surface of the copper wiring layer where light reflection is particularly desired to be suppressed. For this reason, it is preferable to have a blackened wiring layer on the surface required to suppress light reflection.
  • the conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5A includes, for example, copper layers 12A and 12B and blackening layers 131A, 132A, 131B, and 132B on both sides of the transparent base 11 as shown in FIG. 2B. , And can be formed from a laminate substrate.
  • the laminated substrate 20B of FIG. 2B is used as an example.
  • the copper layer 12A and the blackening layers 131A and 132A on the one surface 11a side of the transparent base material 11 are arranged in the Y-axis direction in FIG.
  • Etching is performed so that a plurality of linear patterns parallel to each other are arranged at predetermined intervals along the X-axis direction.
  • the X-axis direction in FIG. 2B means a direction parallel to the width direction of each layer.
  • the Y-axis direction in FIG. 2B means a direction perpendicular to the paper surface in FIG. 2B.
  • the copper layer 12B and the blackening layers 131B and 132B on the other surface 11b side of the transparent substrate 11 are arranged in the Y-axis direction with a plurality of linear patterns parallel to the X-axis direction in FIG. Etching is performed so as to be disposed along the line.
  • the conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5A can be formed.
  • the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the etching of the copper layers 12A and 12B and the blackening layers 131A, 132A, 131B, and 132B may be performed simultaneously.
  • the laminated substrate 10B shown in FIG. 1B is used instead of the laminated substrate 20B in FIG. 2B. Similarly, it can be produced by etching.
  • FIG. 4 can be formed by using two laminated substrates shown in FIG. 1A or FIG. 2A.
  • a case where the two laminated substrates 20A shown in FIG. 2A are formed will be described as an example.
  • the copper layer 12 and the blackened layers 131 and 132 are respectively arranged in the X-axis direction. Etching is performed so that a plurality of parallel linear patterns are arranged along the Y-axis direction at predetermined intervals.
  • the conductive substrate provided with the mesh-like wiring by laminating the two laminated substrates which are oriented so that the linear patterns formed on each laminated substrate by the above etching process cross each other It can be.
  • the two laminated substrate layers that is, the surfaces to be bonded when the conductive substrates are bonded.
  • the surface 132a of the second blackening layer 132 in FIG. 2A and the surface 11b of the transparent substrate 11 on which the copper layer 12 or the like is not laminated are bonded together so that the structure shown in FIG. 5B is obtained. You can also.
  • the surfaces 11b in FIG. 2A where the copper layer 12 or the like of the transparent base material 11 is not laminated can be bonded together so that the cross section has the structure shown in FIG. 5A.
  • the wiring width and the distance between the wirings in the conductive substrate having the mesh-like wiring shown in FIGS. 4, 5A, and 5B are not particularly limited. Can be selected accordingly.
  • 5 ⁇ / b> A, and 5 ⁇ / b> B show an example in which a mesh-like wiring (wiring pattern) is formed by combining linear metal wirings, but the present invention is not limited to such a form.
  • the metal wiring constituting the pattern can have any shape.
  • the shape of the metal wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display. .
  • a conductive substrate having a mesh-like wiring composed of two layers of metal wiring can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
  • Method for producing conductive substrate Next, a configuration example of the method for manufacturing the conductive substrate according to the present embodiment will be described.
  • the manufacturing method of the conductive substrate of this embodiment is as follows: It has a transparent substrate and a metal laminate formed on at least one surface of the transparent substrate, and the metal laminate was laminated with a copper layer and a blackening layer containing nickel and copper
  • the laminated substrate having the structure can have an etching step of etching the metal laminated body to form a metal wiring. And an etching process can have the following steps in that order.
  • a laminate substrate having a transparent substrate 11 and a metal laminate 24 formed on at least one surface of the transparent substrate 11 is prepared.
  • the metal laminate 24 can have a copper layer 12 and blackening layers 131 and 132.
  • 6A shows an example using the laminated substrate 20A shown in FIG. 2A already described, the configuration of the laminated substrate is not limited to such a form. It is also possible to use a laminate substrate having the other configuration described so far, for example, the laminate substrate shown in FIGS. 1A, 1B, and 2B.
  • a resist having a shape corresponding to the pattern of the metal wiring formed on the other surface 24b located on the opposite side to the one surface 24a facing the transparent substrate of the metal laminate 24. 61 can be formed (resist formation step).
  • the formation method of the resist 61 is not particularly limited.
  • a photosensitive dry film resist is attached to the other surface 24b of the metal laminate 24 by a laminating method to form a photosensitive resist layer.
  • ultraviolet rays are irradiated through a photomask having a wiring pattern of metal wirings formed on the photosensitive resist layer to be exposed.
  • the resist 61 having the opening 611 can be formed by bringing the photosensitive resist layer into contact with the developer and dissolving the portion not irradiated with ultraviolet rays.
  • a developing solution For example, sodium carbonate aqueous solution can be used.
  • substrate which has a metal laminated body on both surfaces of transparent base
  • transparent base of each metal laminated body is used.
  • a resist can be formed on the surface opposite to the surface facing the material, and the following etching process can be performed.
  • the first etching step can be performed using the resist 61.
  • the metal laminate 24 can be etched using a first etching solution containing one or more selected from iron chloride, hydrogen peroxide solution, sulfuric acid, and hydrochloric acid.
  • the first etching solution can be supplied from the upper surface of the resist 61. Alternatively, it can be carried out by immersing the laminate substrate in the first etching solution.
  • a metal wiring 64 having a copper wiring layer 62 and blackened wiring layers 631, 632 having a shape corresponding to the pattern of the formed resist 61 is formed. Can be formed.
  • residues 65 such as blackening layers 131 and 132 may be generated in the openings 641 between the metal wirings 64 as shown in FIG. 6B.
  • the residue 65 is generated in the opening 641 of the metal wiring 64, the transparent substrate 11 cannot be directly exposed to the opening 641, and the transparent substrate 11 is colored by the residue 65, and the conductive substrate is formed.
  • the visibility of the display may be reduced.
  • the second etching step can be performed after the first etching step is performed.
  • the specific conditions of the water washing step are not particularly limited, and the conductive substrate can be supplied into a water washing tank containing water and washed with water. Further, for example, water can be sprayed on the surface of the conductive substrate for cleaning.
  • a draining step for removing water adhering to the conductive substrate, a drying step, and the like can be performed as necessary.
  • the residue 65 between the metal wirings 64 can be etched and removed using a second etching solution that is composed of hydrochloric acid and water and has a pH of 2.5 or less.
  • the metal laminate 24 can be etched to form a conductive substrate having metal wiring 64 having a shape corresponding to a desired wiring pattern.
  • the residue 65 is generated in the opening 641 between the metal wirings 64 and the residue 65 remains in the opening between the metal wirings 64 as described above, when the conductive substrate is used for a touch panel, This is a problem that causes the visibility of the display to decrease.
  • the residue generated between the metal wirings 64 can be etched and removed using the second etching solution.
  • the second etching solution is preferably composed of hydrochloric acid and water as described above. This is because the residue 65 is mainly caused by the blackening layers 131 and 132 containing nickel and copper, and the residue 65 also contains nickel and copper as main components. Is increasing. For this reason, the residue 65 can be more reliably removed by using an etching solution comprising hydrochloric acid and water as the second etching solution. In addition, the second etching solution is preferable because the reactivity with the residue 65 is increased and the residue 65 can be more reliably removed by setting the pH to 2.5 or less.
  • the lower limit value is not particularly limited, but in the second etching step, the metal wiring formed in the first etching step is applied to the metal wiring. In order to suppress damage, it can be set to 1.0 or more, for example.
  • the blackening layer is a layer containing nickel and copper
  • the second etching solution is made of hydrochloric acid and water, and an etching solution having a pH of 2.5 or less is used, thereby opening the metal wiring. It is possible to more reliably remove the residue generated in the part. For this reason, the electroconductive board
  • the transparent base material may appear yellow, and the b * of the transparent base material 11 exposed from between the metal wirings may be larger than 1.0.
  • b * of the transparent base material 11 exposed from between metal wiring can be 1.0 or less.
  • the second etching step can be performed in the same manner as in the first etching step except that the second etching solution is used as the etching solution.
  • the second etching solution can be supplied from the upper surface of the resist 61.
  • the laminate substrate that has finished the first etching step can be immersed in the second etching solution.
  • a conductive substrate including a copper wiring layer 62 having a pattern corresponding to the resist 61 and a metal wiring 64 having blackened wiring layers 631 and 632 on the transparent base material 11; The residue 65 existing in the opening 641 between the metal wirings 64 can be removed.
  • the resist can be removed (resist removal step).
  • the method for removing the resist is not particularly limited, but the photosensitive resist can be peeled off and removed using, for example, an aqueous sodium hydroxide solution.
  • an aqueous sodium hydroxide solution As a result, as shown in FIG. 6D, a conductive substrate having the metal wiring 64 including the blackened wiring layers 631 and 632 and the copper wiring layer 62 on the transparent base material 11 can be obtained.
  • substrate of this embodiment can further have arbitrary processes as needed.
  • it can have a laminated body board manufacturing process which manufactures a laminated body board used for an etching process explained so far.
  • laminate substrate manufacturing process The laminate substrate manufacturing process can include the following steps.
  • a laminated body board manufacturing process is corresponded to the manufacturing method of the laminated body board
  • a copper layer forming step of forming a copper layer on at least one surface of the transparent substrate A blackening layer forming step of forming a blackening layer on at least one surface of the transparent substrate;
  • the order of lamination when the copper layer and the blackened layer are arranged on the transparent substrate is not particularly limited. Further, a plurality of copper layers and blackening layers can be formed. For this reason, the order in which the copper layer forming step and the blackened layer forming step are performed and the number of times of performing the steps are not particularly limited, and any number of times and timings may be selected according to the structure of the laminate substrate to be formed. Can be implemented.
  • a copper layer can be formed on at least one surface of the transparent substrate.
  • the kind of transparent base material used for the copper layer forming step or the blackened layer forming step is not particularly limited, but as described above, a resin substrate (resin film) that transmits visible light, or a glass substrate Etc. can be preferably used.
  • the transparent base material can be cut into an arbitrary size in advance if necessary.
  • the copper layer preferably has a copper thin film layer as described above.
  • the copper layer can also have a copper thin film layer and a copper plating layer.
  • a copper layer formation step can have a copper thin film layer formation step which forms a copper thin film layer, for example with a dry-type plating method.
  • the copper layer forming step includes a copper thin film layer forming step for forming a copper thin film layer by a dry plating method, and a copper plating layer formed by an electrolytic plating method which is a kind of wet plating method using the copper thin film layer as a power feeding layer. And a copper plating layer forming step.
  • the dry plating method used in the copper thin film layer forming step is not particularly limited, and for example, an evaporation method, a sputtering method, an ion plating method, or the like can be used.
  • a vapor deposition method a vacuum vapor deposition method can be used preferably.
  • the dry plating method used in the copper thin film layer forming step it is more preferable to use the sputtering method because the film thickness is particularly easy to control.
  • the conditions in the copper plating layer forming step by the wet plating method that is, for example, the conditions of the electrolytic plating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted.
  • a copper plating layer can be formed by supplying a base material on which a copper thin film layer is formed in a plating tank containing a copper plating solution and controlling the current density and the conveyance speed of the base material.
  • the blackened layer forming step is a step of forming a blackened layer on at least one surface side of the transparent substrate as described above.
  • the means for forming the blackening layer is not particularly limited, and any method can be selected as long as it can be formed so as to contain nickel and copper.
  • the blackening layer is preferably formed directly on the upper surface of another member such as a transparent substrate and / or a copper layer without using an adhesive.
  • a film forming method can be selected depending on the structure of the underlying layer when forming the blackened layer, and as the blackened layer forming method, for example, a wet plating method or a dry plating method is used. be able to.
  • the blackened layer can also contain, for example, oxygen.
  • oxygen can be added to an atmosphere in which the blackening layer is formed, for example, an inert gas. Argon or the like can be used as the inert gas.
  • a plurality of blackening layers included in the same laminate substrate may be formed by the same film formation method or by different film formation methods.
  • a film may be formed. (Lamination process) Further, as described above, for example, two laminated substrates having a copper layer and a blackened layer are prepared on one surface side of the transparent substrate 11 shown in FIGS. After patterning to be metal wiring, it can be bonded to form a conductive substrate having mesh wiring.
  • a bonding step of bonding the two patterned laminate substrates can be included.
  • the method for bonding the two patterned laminate substrates is not particularly limited, and for example, the bonding can be performed using an adhesive or the like.
  • substrate of this embodiment was demonstrated.
  • the method for manufacturing the conductive substrate of the present embodiment it is possible to reduce the residue of the opening between the metal wirings.
  • the transparent base material exposed between metal wirings has high visible light transmittance, and can provide the electroconductive board
  • Experimental examples 1-1 to 1-3 are examples, and experimental examples 1-4 to 1-6 are comparative examples.
  • (Experimental example 1-1) A conductive substrate having the cross-sectional structure shown in FIG. 5A was produced by the following procedure.
  • (1) Laminate substrate manufacturing process (1-1) First blackened layer forming step First, on one side of a transparent base material made of polyethylene terephthalate resin (PET) having a thickness of 100 ⁇ m and on the opposite side of one side. The first blackening layer was formed on both surfaces of the other surface.
  • PET polyethylene terephthalate resin
  • the visible light transmittance of the transparent base material made of polyethylene terephthalate resin used as the transparent base material was evaluated by the method prescribed in JIS K 7361-1, and found to be 97%.
  • the first blackening layer was formed by sputtering using a nickel-copper alloy target containing 70% by mass of nickel and 30% by mass of copper.
  • the transparent substrate from which moisture was removed by heating to 60 ° C. in advance was set in the chamber of the sputtering apparatus. Then, after evacuating the chamber to 1 ⁇ 10 -4 Pa, in a chamber, after a while introducing a mixed gas of argon and oxygen 0.3 Pa, a film was formed.
  • argon gas and oxygen gas were mixed and used so that oxygen content in mixed gas might be 30 volume%.
  • the first blackening layer 131 was formed to a thickness of 20 nm.
  • Copper layer forming step (copper thin film layer forming step) Subsequently, a copper thin film layer was formed as a copper layer on each first blackened layer of the transparent substrate on which the first blackened layer was formed.
  • the copper layer was sputtered in the same manner as in the case of the first blackening layer except that a copper target was used as a target, and argon gas was used instead of a mixed gas of argon gas and oxygen gas.
  • a copper layer having a thickness of 500 nm was formed on the upper surface of the first blackened layer by the method.
  • (1-3) Second Blackening Layer Formation Step Subsequently, a second blackening layer was formed on each copper layer.
  • the second blackened layer forming step was performed under the same conditions as in the first blackened layer forming step, and a second blackened layer having a thickness of 20 nm was formed on the copper layer.
  • the metal laminates 24A and 24B are formed by laminating first blackened layers 131A and 131B, copper layers 12A and 12B, and second blackened layers 132A and 132B in this order.
  • the produced laminate substrate was cut into 100 mm squares and subjected to the following etching process.
  • the metal laminates 24A and 24B are located on the opposite side to the one surface facing the transparent base material 11.
  • a resist having a shape corresponding to the pattern of the metal wiring formed on the other surface A and surface B was formed.
  • the conductive substrate shown in FIGS. 4 and 5A is manufactured, and a plurality of linear metal wirings 44A parallel to the Y-axis are provided on one surface 11a side of the transparent base material 11, and the other side. On the surface 11b side, a plurality of linear metal wirings 44B parallel to the X axis are formed. For this reason, the resist was also formed to have a shape corresponding to the metal wiring.
  • a photosensitive dry film resist is applied to the surfaces A and B of the metal laminates 24A and 24B of the laminate substrate 20B shown in FIG. 2B by a laminating method to form a photosensitive resist layer.
  • ultraviolet rays are irradiated through a photomask having a wiring pattern of metal wirings formed on the photosensitive resist layer to be exposed.
  • the photosensitive resist layer was brought into contact with a 1% by mass aqueous sodium carbonate solution, and the portion not irradiated with ultraviolet rays was dissolved to form a resist pattern.
  • a first etching step was performed using the produced resist.
  • the metal laminates 24A and 24B were etched using a first etching solution composed of 5% by mass of ferric chloride, 3% by mass of hydrochloric acid, and the balance of ion-exchanged water.
  • the metal laminates 24A and 24B are etched by immersing the laminate substrate on which the resist is placed in the first etching solution heated to a temperature of 30 ° C. for 30 seconds. The transparent substrate was exposed between the formed metal wirings.
  • (2-3) Water washing step After the first etching step, the laminated substrate patterned in a water washing tank containing a sufficient amount of ion-exchanged water is washed with running water for 10 seconds to remove the attached first etching solution. did. After washing with water, the adhering water was drained, dried and subjected to the second etching step.
  • Second Etching Step After the rinsing step, the residue between the metal wirings was etched using a second etching solution consisting of hydrochloric acid and ion-exchanged water and having a pH of 2.5.
  • the second etching step was performed by immersing the patterned laminate substrate after the water washing step in the second etching solution at room temperature (23 ° C.) for 10 seconds.
  • Resist removal step After completion of the second etching step, the resist was stripped and removed using a 4 mass% sodium hydroxide aqueous solution. Then, after removing the resist, the conductive substrate obtained in the same manner as in the water washing step was washed with ion-exchanged water, drained and dried.
  • the conductive substrate obtained by carrying out the above steps was evaluated for the visible light transmittance and b * of the transparent substrate exposed in the opening between the metal wirings. The results are shown in Table 1.
  • Example 1-2 Experimental Example 1-3
  • the amount of hydrochloric acid added was adjusted so that the pH of the second etching solution used in the second etching step was the value shown in Table 1 for each experimental example, the same procedure as in Experimental example 1-1 was performed.
  • a conductive substrate was prepared and evaluated. The results are shown in Table 1.
  • Example 1-4 A conductive substrate was prepared and evaluated in the same manner as in Experimental Example 1-1 except that the second etching step was not performed and only the water washing step was performed. The results are shown in Table 1.
  • Experimental Examples 2-1 to 2-5 are all comparative examples.
  • Example 2-1 to Experimental example 2-5 As the second etching solution used in the second etching step, an etching solution composed of sulfuric acid and ion-exchanged water is used, and sulfuric acid is adjusted so that the pH of the etching solution becomes the value shown in Table 2 for each experimental example.
  • a conductive substrate was prepared and evaluated in the same manner as in Experimental Example 1-1 except that the addition amount of was adjusted. The results are shown in Table 2.
  • the second etching solution having a pH of 2.5 or less is used in the second etching step.
  • the visible light transmittance of the transparent substrate between the metal wirings could be 90.0% or more.
  • the 2nd etching liquid whose pH exceeds 2.5 it has confirmed that it was as low as about 89%.

Abstract

L'invention concerne un substrat conducteur qui comprend une base transparente et des lignes de câblage métalliques qui sont formées sur au moins une surface de la base transparente, et est caractérisé en ce que : chaque ligne de câblage métallique possède une structure dans laquelle une couche de câblage en cuivre et une couche de câblage noircie contenant du nickel et du cuivre sont stratifiées ; et la base transparente exposée entre les lignes de câblage métalliques possède une transmittance de la lumière visible de 90 % ou plus et une valeur b* de 1,0 ou moins.
PCT/JP2017/014575 2016-04-18 2017-04-07 Substrat conducteur et procede de fabrication d'un substrat conducteur WO2017183489A1 (fr)

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JP7101113B2 (ja) 2022-07-14
TWI728095B (zh) 2021-05-21
TW201806754A (zh) 2018-03-01
CN108700969B (zh) 2022-04-08
JPWO2017183489A1 (ja) 2019-02-21

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