JP2017118069A - Electrolytic plating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic plating method which allows for desired electrolytic plating even when a low resistance part to be plated relatively easily and a high resistance part not to be plated easily exist on a plated material, especially allows for desired plating on a conductive fine wire when including a pattern consisting of an aggregation of conductive fine wires as the conductive pattern.SOLUTION: In an electrolytic plating method performing electrolytic plating in a plating bath 2 while transporting a plated material 1 having a conductive pattern 12 on a long-sized sheet base material 11, the conductive pattern 12 has a plurality of parts of different electrical resistance, and electrolytic plating is performed by arranging a plurality of anodes 3a, 3b in one plating bath 2, and adjusting the application conditions thereto independently.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrolytic plating method, and more particularly, even when a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated exists on a material to be plated. In particular, the present invention relates to an electrolytic plating method capable of performing desired plating on a conductive thin wire when the conductive pattern includes a pattern made of an assembly of conductive thin wires.

  Patent Documents 1 and 2 disclose that an anode is disposed in a plating bath, a cathode roll is brought into contact with a material to be transported, power is supplied, and the material to be plated is subjected to electrolytic plating.

JP-A-53-87941 JP-A-63-183192

  However, in the conventional technique, it is difficult to perform stable electrolytic plating when there are a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated. is there. In particular, when the conductive pattern includes a pattern made of an aggregate of conductive thin wires, it is difficult to perform desired plating on the conductive thin wires.

  Accordingly, an object of the present invention is to perform desired electrolytic plating even when a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated exists on the material to be plated. In particular, it is an object of the present invention to provide an electrolytic plating method capable of performing desired plating on a conductive thin wire when the conductive pattern includes a pattern made of an assembly of conductive thin wires.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1.
An electrolytic plating method for electrolytic plating in a plating bath while conveying a material to be plated having a conductive pattern on a long sheet substrate,
The conductive pattern has a plurality of portions having different electric resistances,
A method of electroplating, wherein a plurality of anodes are disposed in one plating bath, and electroplating is performed by independently adjusting application conditions to the plurality of anodes.
2.
2. The electrolytic plating method according to 1 above, wherein at least one of the anodes is adjusted to a constant voltage.
3.
3. The electrolytic plating method according to 2, wherein at least one of the anodes is adjusted to a constant voltage, and at least one of the anodes is adjusted to a constant current.
4).
4. The electrolytic plating method according to 3 above, wherein the anode adjusted to a constant voltage is disposed upstream of the anode adjusted to a constant current in the conveying direction of the material to be plated.
5.
The distance between at least one of the anodes adjusted to a constant voltage and the material to be plated is shorter than the distance between the other anodes and the material to be plated. The electrolytic plating method described.
6).
The material to be plated is transported from the cathode roll in the air to the material to be plated which is not plated in the plating bath while the material to be plated is conveyed over at least the air cathode roll. 6. The electrolytic plating method as described in any one of 1 to 5 above, wherein the electroplating is performed by supplying power in the opposite direction.
7).
7. The electrolytic plating method according to any one of 1 to 6, wherein the electrical resistance of the conductive pattern on the long sheet base material is different in the longitudinal direction of the long sheet base material.
8).
2. The electrolytic plating method according to 1 above, wherein the application conditions to the plurality of anodes are independently adjusted based on positional information of the material to be plated.
9.
9. The electrolytic plating method according to 1 or 8, wherein the application conditions to the plurality of anodes are independently adjusted by a predetermined program.

  According to the present invention, a desired electrolytic plating can be performed on a material to be plated even when there is a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated. In particular, when the conductive pattern includes a pattern made of an aggregate of conductive thin wires, an electrolytic plating method can be provided that can perform desired plating on the conductive thin wires.

The schematic block diagram which illustrates notionally an example of the electroplating apparatus for enforcing the electroplating method of this invention A plan view illustrating an example of a material to be plated before being subjected to electrolytic plating The schematic block diagram which illustrates notionally other examples of the electroplating apparatus for enforcing the electroplating method of this invention The schematic block diagram which illustrates notionally further another example of the electroplating apparatus for enforcing the electroplating method of this invention The figure explaining an example of the method of forming a mesh-like electrically conductive film

  Below, the form for implementing this invention is demonstrated.

  The electrolytic plating method of the present invention can be preferably used when electrolytic plating is performed on a material to be plated having a conductive pattern on a long sheet substrate. In particular, it can be preferably used when electrolytic plating is carried out in a plating bath while conveying the material to be plated.

  In the present invention, the conductive pattern has a plurality of portions having different electric resistances, and a plurality of anodes are arranged in one plating bath, and an application condition to the plurality of anodes is independently adjusted to perform electrolysis. One feature is plating.

  As a result, even when a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated exists on the material to be plated, desired electrolytic plating can be performed. In the case where the conductive pattern includes a pattern made of an aggregate of conductive thin wires, an effect that desired plating can be applied to the conductive thin wires can be obtained.

  Hereinafter, the present invention will be described in more detail by taking as an example the case of manufacturing a touch panel sensor by an electrolytic plating method.

  A first aspect of the electrolytic plating method of the present invention will be described with reference to FIGS.

  FIG. 1 is a schematic configuration diagram conceptually illustrating an example of an electrolytic plating apparatus for carrying out the electrolytic plating method of the present invention, and FIG. 2 illustrates an example of a material to be plated before being subjected to electrolytic plating. It is a top view.

  In FIG. 1, 1 is a material to be plated, 2 is a plating bath, 3a and 3b are anodes, 4 is a cathode roll constituting a cathode, and 5 is a transport roll.

  Here, the electroplating apparatus applies a voltage from a power supply device (not shown) to the anode 3 and the cathode roll 4 while conveying the material 1 to be plated, which is stretched over a plurality of conveyance rolls 5, in a predetermined conveyance direction α. The material to be plated 1 is electrolytically plated in a plating bath 2.

  The material to be plated 1 has a conductive pattern 12 made of a conductive material on a long sheet base material 11. The material to be plated 1 is an object to be subjected to electrolytic plating. Specifically, a plating film is formed on the conductive pattern 12 on the long sheet substrate 11 by electrolytic plating.

  As shown in FIG. 2, in the material to be plated 1, a plurality of units 13 for constituting a touch panel sensor are provided on the long sheet substrate 11 along the longitudinal direction of the long sheet substrate 11. Has been placed.

  The unit 13 includes a plurality of strip-like mesh-like conductive films 14 arranged side by side. The mesh-like conductive film 14 is formed by intersecting a plurality of conductive thin wires 15 with each other. Further, wirings 16 are connected to the mesh-like conductive film 14 respectively. The unit 13 includes the mesh-like conductive film 14 and the wiring 16.

  The mesh-like conductive film 14 can be used as a position detection electrode (for example, an X electrode or a Y electrode) in the touch panel sensor, and the wiring 16 is used to connect the mesh-like conductive film 14 that is the position detection electrode to a control circuit (not shown). be able to.

  The mesh conductive film 14 and the wiring 16 are made of a conductive material patterned in a predetermined shape. The conductive pattern 12 is formed by arranging a plurality of units 13 including the mesh-like conductive film 14 and the wiring 16 along the longitudinal direction of the long sheet base material 11.

  Reference numeral 17 denotes an auxiliary conductive portion provided on the long sheet base material 11 for electrolytic plating. The auxiliary conductive portion 17 is in contact with the cathode roll 4 shown in FIG. It is configured to assist. Here, power is supplied from the cathode roll 4 to the wiring 16 of each unit 13 and the mesh-like conductive film 14 connected to the wiring 16 through the auxiliary conductive portion 17. The auxiliary conductive portion 17 can be removed after the electrolytic plating is completed.

  Here, in order to provide the touch panel sensor with sufficient translucency and low visibility (property of being visually recognized), the line width of the conductive thin wire 15 constituting the mesh-like conductive film 14 is larger than the line width of the wiring 16. Is also small. Thereby, the electrical resistance of the mesh-like conductive film 14 is higher than the electrical resistance of the wiring 16. That is, the conductive pattern 12 has a plurality of portions having different electric resistances.

  The line width of the conductive thin wires 15 constituting the mesh-like conductive film 14 is not particularly limited, and can be, for example, in the range of 1 μm to 20 μm. Further, the line width of the wiring 16 is not particularly limited, and can be set in a range of 30 μm to 200 μm, for example.

  A relatively high resistance mesh-like conductive film 14 and a relatively low resistance wiring 16 are alternately arranged along the longitudinal direction of the long sheet base material 11, thereby providing a long sheet base material. The electrical resistance of the conductive pattern 12 on 11 is different in the longitudinal direction of the long sheet substrate 11.

  From the viewpoint of remarkably exhibiting the effect of the present invention, as described above, the electrical resistance of the conductive pattern 12 on the long sheet substrate 11 is different in the longitudinal direction of the long sheet substrate 11. It is preferable.

  For the plating bath 2, an aqueous solution containing plating metal ions can be preferably used. Preferred examples of the plating metal include copper, nickel, and chromium.

  The anodes 3a and 3b are respectively arranged in the plating bath 2 so as to face the conductive pattern 12 provided on the lower surface side of the material 1 to be plated.

  In the present invention, a plurality of (two in the example of FIG. 1) anodes 3a and 3b are arranged in one plating bath 2, and the application conditions to the plurality of anodes 3a and 3b are independently adjusted to perform electrolytic plating. One feature is to do.

  As a result, it is possible to suitably perform electroplating even on a conductive pattern having a high electric resistance. Particularly, electroplating is also preferably performed on a conductive pattern having a high resistance portion and a low resistance portion. The effect of being able to be obtained. In particular, when the conductive pattern 12 includes a pattern made of an aggregate of the conductive thin wires 15 such as the mesh-like conductive film 14, an effect that desired plating can be applied to the conductive thin wires 15 is obtained. .

  As the application condition described above, it is preferable to adjust at least one of the plurality of anodes 3a and 3b to a constant voltage. Thereby, electrolytic plating can be quickly applied to the wiring 16 which is a low resistance portion.

  Further, as the application condition described above, it is preferable that at least one of the plurality of anodes 3a and 3b is adjusted to a constant voltage and at least one anode 3b is adjusted to a constant current. As a result, the wiring 16 which is the low resistance portion is quickly subjected to electrolytic plating by the anode 3a adjusted to a constant voltage, and the mesh-like conductive film 14 which is a high resistance portion and the low resistance are controlled by the anode 3b adjusted to a constant current. The effect that the difference of the plating amount with respect to the wiring 16 which is a part can be reduced is obtained.

  From the viewpoint of more prominently exhibiting the above-described effect by combining the constant voltage and the constant current, as shown in FIG. 1, the anode 3a that is adjusted to a constant voltage is more material to be plated than the anode 3b that is adjusted to a constant current. 1 is preferably arranged upstream of the conveyance direction α.

  Further, from the viewpoint of more prominently exhibiting the above-described effect by combining a constant voltage and a constant current, as shown in FIG. 1, the distance between the anode 3a to be adjusted to a constant voltage and the material to be plated 1 is set to other values. It is preferable that the distance between the anode 3b and the material 1 to be plated is shorter.

  Next, power supply from the cathode roll 4 will be described in detail.

  As shown in FIG. 1, the material to be plated 1 is stretched over the cathode roll 4, similarly to the other transport rolls 5. The cathode roll 4 is configured to convey the material 1 to be plated, to be in contact with the material 1 to be plated and to be electrically connected to the conductive pattern 12 and to supply power to the conductive pattern 12. The electrical connection between the cathode roll 4 and the conductive pattern 12 can be made, for example, by contacting the cathode roll 4 with the conductive pattern 12 and / or the auxiliary conductive portion 17 of the material to be plated 1.

  Here, the cathode roll 4 is disposed in the air on the outlet side of the plating bath 2. As a result, the material to be plated 1 in the plating bath 2 is subjected to electrolytic plating by supplying power from the air cathode roll 4 in the direction opposite to the conveying direction α of the material 1 to be plated. Yes. The term “in the air” means not in the plating bath 2.

  As described above, by supplying power in the direction opposite to the conveying direction α of the material to be plated 1, the material to be plated after the plating material 1 in the plating bath 2 that has not been plated is plated. It is possible to supply power via 1. Therefore, even when the electric resistance of the conductive pattern 12 of the material to be plated 1 is high, an effect of performing suitable electrolytic plating can be obtained.

  In the above description, as an example of independently adjusting the application conditions to the plurality of anodes, the case where at least one anode is adjusted to a constant voltage and at least one anode is adjusted to a constant current has been mainly shown. It is not limited to this.

  For example, the plurality of anodes can be adjusted to a constant voltage, and the set voltage of at least one anode can be adjusted to a value different from the set voltages of other anodes. In this case, it is preferable to arrange the anode having a high set voltage upstream of the anode having the low set voltage in the transport direction α.

  In addition, for example, the plurality of anodes can be adjusted to a constant current, and the set current of at least one anode can be adjusted to a value different from the set current of other anodes. In this case, it is preferable to arrange the anode having a large set current upstream of the anode having the small set current in the transport direction α.

  Next, a second aspect of the electrolytic plating method of the present invention will be described with reference to FIG.

  FIG. 3 is a schematic configuration diagram conceptually illustrating another example of an electrolytic plating apparatus for carrying out the electrolytic plating method of the present invention. 3, the same reference numerals as those in FIGS. 1 and 2 have the same configuration, and the description made with reference to FIGS. 1 and 2 can be used.

  In the second aspect, electrolytic plating is performed by independently adjusting the application conditions to the plurality of anodes 3a and 3b based on the positional information of the material 1 to be plated. The material to be plated 1 has the same configuration as that described with reference to FIG.

  In the example of FIG. 3, the anodes 3a and 3b and the material to be plated 1 are arranged so as to have the same distance.

  FIG. 3A shows a state in which the mesh-like conductive film 14 that is a high resistance portion is close to the anode 3a, and FIG. 3B shows that the mesh-like conductive film 14 that is a high resistance portion is close to the anode 3b. The approaching state is shown.

  In this embodiment, as shown in FIG. 3A, voltage is applied to the anode 3a while the mesh-like conductive film 14 which is a high resistance portion is approaching the anode 3a (in FIG. 3). The anode to which voltage is applied is marked “ON”). In this state, no voltage is applied to the anode 3b to which the mesh-like conductive film 14 is not approaching (in FIG. 3, “OFF” is given to the anode to which no voltage is applied).

  Then, the material to be plated 1 is further transported from the state of FIG. 3A, and as shown in FIG. 3B, the anode 3b is in contact with the mesh-like conductive film 14 which is a high resistance portion. A voltage is applied to 3b. In this state, no voltage is applied to the anode 3a to which the mesh-like conductive film 14 is not approaching (in FIG. 3, “OFF” is given to the anode to which no voltage is applied).

  As a result, the electrolytic plating is preferentially applied to the high resistance portion, so that the difference in plating amount between the high resistance portion and the low resistance portion can be reduced.

  An example of adjusting application conditions for performing preferential electrolytic plating on the high resistance portion as described above will be described. Here, the anode 3a will be described.

  First, position information of the material to be plated 1 is acquired. This position information can include, for example, information for specifying the position of a specific part in the material to be plated 1. The specific part may be, for example, the top of the material to be plated 1, a specific pattern on the material to be plated 1, or a detection marker provided in advance on the material to be plated 1. Since the position changes as the material to be plated 1 is conveyed, it is preferable to acquire the position information continuously or intermittently at a predetermined timing.

  The specific method for acquiring the position information of the material to be plated 1 is not particularly limited. For example, the method for acquiring the position information of the material to be plated 1 based on the image data obtained by imaging the material to be plated 1, the conveyance distance of the material to be plated 1 The acquisition method based on the relationship between the conveyance speed and conveyance time of the to-be-plated material 1 can be mentioned.

  Based on the acquired position information of the material 1 to be plated, the distance between the high resistance portion of the material 1 to be plated and the anode 3a is calculated. Then, when it is determined that the distance is equal to or less than a preset threshold value, voltage application to the anode 3a is started, and when it is determined that the distance exceeds a preset threshold value, the anode is The application condition to the anode 3a can be adjusted so as to stop the voltage application to 3a. As a result, the application condition to the anode 3a changes with time.

  In another aspect, the distance between the low resistance portion of the material to be plated 1 and the anode 3a is calculated based on the acquired position information of the material to be plated 1. When it is determined that the distance exceeds a preset threshold value, voltage application to the anode 3a is stopped, and when it is determined that the distance is equal to or less than the preset threshold value, The application condition to the anode 3a can be adjusted so as to start the voltage application to 3a.

  In the above description, the voltage application to the anode 3a is turned on and off as the application condition to the anode 3a. However, the present invention is not limited to this, and the adjustment of the voltage or current applied to the anode 3a is adjusted. May be performed.

  Although the anode 3a has been mainly described above, the same adjustment can be performed on the anode 3b independently of the anode 3a. In this way, by performing electroplating by independently adjusting the application conditions to the plurality of anodes 3a and 3b based on the position information of the material 1 to be plated, electroplating to the low resistance portion is suppressed, and as a result, Preferential electrolytic plating can be performed on the high resistance portion.

  The adjustment (also referred to as control) of the application conditions as described above can be performed by a predetermined program. It is preferable to automatically control the application conditions using a computer that executes a predetermined program.

  Next, with reference to FIG. 4, the present invention will be described in more detail by taking as an example a case where an electrolytic plating apparatus configured to vertically convey a material to be plated is used as a third aspect.

  FIG. 4 is a schematic configuration diagram conceptually illustrating still another example of the electrolytic plating apparatus for carrying out the electrolytic plating method of the present invention. 4, the same reference numerals as those in FIGS. 1 to 3 have the same configuration, and the description made with reference to FIGS. 1 to 3 can be used.

  FIG. 4A shows a state in which the electrolysis apparatus is viewed in plan, and FIG. 4B shows a state in which the electrolysis apparatus is viewed from the side.

  In the example of FIG. 4, the material to be plated 1 is provided with conductive patterns 12 similar to those shown in FIG. 2 on both sides of the long sheet base material 11. The electrolytic plating apparatus is configured to perform electrolytic plating on the conductive patterns 12 on both sides while vertically conveying the material 1 to be plated.

  The material 1 to be plated is transported into the plating bath 2 while being sandwiched between a pair of transport rolls 5, 5 provided on one side of the plating bath 2, and is paired on the other side of the plating bath 2. It is configured to be conveyed to the outside of the plating bath 2 while being sandwiched between the conveying rolls 5 and 5.

  The pair of transport rolls 5, 5 provided respectively on one side surface and the other side surface can be configured to be sealable so that the plating solution does not leak from the plating bath 2.

  The to-be-plated material 1 conveyed outside the plating bath 2 is further configured to be sandwiched and conveyed by cathode rolls 4 and 4 provided in the air.

  In this way, even when the material to be plated 1 is conveyed vertically, power can be supplied in the direction opposite to the conveying direction α of the material to be plated 1 as in the example of FIGS. That is, power can be supplied to the material 1 to be plated in the plating bath 2 through the material 1 after plating. Here, the electroplating is efficiently performed on the conductive patterns 12 on both sides of the long sheet base material 11 in one plating bath 2 by sandwiching the material to be plated 1 between the cathode rolls 4 and 4. I try to do it.

  Here, in one plating bath 2, four anodes 3 a to 3 d are arranged on one surface side of the material 1 to be plated, and four anodes 3 a ′ to 3 d ′ are arranged on the other surface side of the material 1 to be plated. ing.

  The anodes 3a and 3b are disposed upstream of the anodes 3c and 3d in the conveyance direction α of the material to be plated 1.

  Of the anodes 3 a and 3 b disposed upstream in the transport direction α, the anode 3 a is disposed above the plating bath 2, and the anode 3 b is disposed below the plating bath 2. That is, in this aspect, the plurality of anodes 3a and 3b are arranged in the width direction of the material to be plated 1 (direction orthogonal to the transport direction α). Therefore, even when the electric resistance of the conductive pattern 12 differs in the width direction of the material to be plated 1, by adjusting the application conditions to the plurality of anodes 3a and 3b independently, in particular in the width direction of the material to be plated 1 In this case, the difference in plating amount between the high resistance portion and the low resistance portion can be reduced.

  As for the anodes 3c and 3d arranged downstream in the transport direction α, the anode 3c is arranged above the plating bath 2, and the anode 3d is arranged below the plating bath 2, so that the above-described anode 3a, Similarly to 3b, it is possible to cope with a case where the electric resistance of the conductive pattern 12 differs in the width direction of the material 1 to be plated.

  The anodes 3a 'to 3d' arranged on the other surface side of the material to be plated 1 have the same positional relationship as the anodes 3a to 3d except that the arrangement surfaces are different.

  Even in this embodiment, by independently adjusting the application conditions to the plurality of anodes 3a to 3d, 3a 'to 3d', even when the low resistance portion and the high resistance portion exist on the material to be plated 1, The effect that a stable electrolytic plating can be performed is obtained.

  For example, as in the first embodiment, a constant voltage and a constant current may be combined as application conditions to the plurality of anodes 3a to 3d, 3a ′ to 3d ′, and the position of the material 1 to be plated is similar to the second embodiment. Based on the information, the application conditions to the plurality of anodes 3a to 3d, 3a 'to 3d' may be adjusted independently.

  As described above, the configuration in which a plurality of anodes are arranged in the width direction of the material to be plated 1 can be preferably applied to the case of horizontal conveyance as in the first aspect and the second aspect.

  In the above description, the case where all of the plurality of anodes are adjusted independently from each other has been mainly shown, but the present invention is not limited to this. For example, the application conditions may be similarly adjusted for an anode group consisting of a plurality of anodes among a plurality of anodes in the plating bath 2. At this time, a plurality of anode groups may be configured, and application conditions may be adjusted independently for one anode group and another anode group, or one or a plurality of anode groups may be configured to provide one anode group. The application conditions may be adjusted independently for the group and the other anodes. This will be described below with reference to FIG. 4 again.

  For example, among the plurality of anodes 3a to 3d and 3a ′ to 3d ′ illustrated in FIG. 4, the plurality of anodes 3a, 3b, 3a ′, and 3b ′ disposed upstream in the conveyance direction α of the material to be plated 1. A first anode group is constituted, and a plurality of anodes 3c, 3d, 3c ′, 3d ′ arranged downstream is constituted by a second anode group, and application conditions are determined by the first anode group and the second anode group. Can be adjusted independently.

  Among the plurality of anodes 3a to 3d, 3a ′ to 3d ′, the plurality of anodes 3a, 3c, 3a ′, which are disposed above the plating bath 2 (one side in the width direction of the material to be plated 1), 3c ′ constitutes a first anode group, and a plurality of anodes 3b, 3d, 3b ′, 3d ′ arranged below (the other side in the width direction of the material to be plated 1) constitutes a second anode group, The application conditions can be adjusted independently for the first anode group and the second anode group.

  Furthermore, among the plurality of anodes 3a to 3d and 3a 'to 3d', a first anode group is constituted by the anodes 3a to 3d disposed on the one surface side of the material 1 to be plated, and the anode disposed on the other surface side. The second anode group is configured by 3a ′ to 3d ′, and the application conditions can be independently adjusted for the first anode group and the second anode group. Thereby, it can respond suitably, especially when the electrical resistance of the conductive pattern 12 differs between the one surface side and the other surface side.

  The configuration example of the anode group is not limited to the above example, and can be appropriately configured according to the electric resistance of the conductive pattern 12 or the like. Further, the anode group has been described using an example of vertical conveyance, but it can be preferably applied to the case of horizontal conveyance.

  In the above description, the case where the two anodes 3c and 3d are installed in the conveyance direction of the material to be plated and the two anodes are installed in the width direction of the material to be plated has been described, but the present invention is not limited to this. It is sufficient that two or more anodes are provided in one plating bath, and their arrangement is not particularly limited.

  In the above description, as a method of supplying power from the cathode to the conductive pattern, a method of supplying power in the direction opposite to the transport direction from the cathode roll disposed outside the plating bath downstream in the transport direction has been mainly shown. Instead, it is sufficient if power can be supplied to the conductive pattern.

  A method of forming the conductive pattern 12 made of a conductive material on the long sheet base material (hereinafter sometimes simply referred to as a base material) 11 is not particularly limited. For example, a printing method or a photolithography method is used. Can be formed. In particular, a printing method is preferable, and an inkjet method can be preferably used.

  In particular, when the mesh conductive film 14 in the conductive pattern 12 is formed, the method described below with reference to FIG. 5 can be preferably used.

  First, as shown to Fig.5 (a), the liquid containing an electroconductive material is provided on the base material 11 in the shape of a line, and the line-shaped liquid 6 is formed. Here, a plurality of line-like liquids 6 are formed in a direction inclined with respect to the longitudinal direction of the base material 11. The line liquids 6 are arranged in parallel at a predetermined interval.

  In forming the line-like liquid 6, a printing method can be preferably used, and an inkjet method is particularly preferable. When the inkjet method is used, a liquid containing a conductive material is ejected as droplets from the nozzles of the inkjet head while moving the inkjet head relative to the substrate, and the ejected droplets are combined on the substrate. Thus, a line-like liquid can be formed. The droplet discharge method of the inkjet head is not particularly limited, and for example, a piezo method or a thermal method can be used.

  Next, as shown in FIG. 5B, the line-shaped liquid 6 is dried to form a conductive thin wire 15 containing a conductive material. Here, when the line-shaped liquid 6 is dried, the conductive material is selectively deposited on the edge of the line-shaped liquid 6 by the internal flow of the line-shaped liquid 6, and the line width is narrower than that of the line-shaped liquid 6. Conductive thin wires 15 are formed. When the conductive material is selectively deposited by the internal flow of the line-like liquid 6, the coffee stain phenomenon can be suitably used. As a result, a parallel line composed of two conductive thin wires 15 parallel to each other can be formed from each line-like liquid 6 along the edge of the line-like liquid 6.

  It is preferable to promote the selective deposition by the internal flow described above by setting the drying conditions of the line-like liquid 6. The drying conditions can be appropriately set by combining a method of heating the surface of the substrate 11 (surface on which the line-shaped liquid is formed) to a predetermined temperature, a method of blowing air, and the like.

  Next, as shown in FIG. 5C, a plurality of further line-shaped liquids 6 are formed in a direction intersecting with the previously formed conductive thin wires 15. The line liquids 6 are arranged in parallel at a predetermined interval.

  Next, as shown in FIG. 5 (d), the line-like liquid 6 is dried to form further conductive fine wires 15. Also here, when the line-shaped liquid 6 is dried, the conductive material is selectively deposited on the edge of the line-shaped liquid 6 by the internal flow of the line-shaped liquid 6 so that the line width is narrower than that of the line-shaped liquid 6. Conductive thin wires 15 are formed.

  In this way, the mesh-like conductive film 14 can be formed by intersecting the plurality of conductive thin wires 15 with each other.

  From the viewpoint of remarkably exhibiting the effects of the present invention, the line width (thickness) of the conductive thin wire 15 is preferably 20 μm or less, and more preferably 10 μm or less. By selectively depositing the conductive material by the internal flow of the line-like liquid 6, the thin conductive thin wire 15 as described above can be suitably formed.

  It is also preferable that the auxiliary conductive portion 17 described with reference to FIG. 1 is composed of a mesh-like conductive film formed by the same method as the method of forming the mesh-like conductive film 14 described with reference to FIG. is there.

  The conductive material constituting the conductive pattern 12 is not particularly limited, and various materials can be used. In particular, as described above, the conductive material is selectively deposited on the edge of the line-shaped liquid 6 by the internal flow of the line-shaped liquid 6 to form the conductive thin line 15 having a line width narrower than that of the line-shaped liquid 6. For example, conductive fine particles, conductive polymers, and the like can be preferably used.

  The conductive fine particles are not particularly limited, but Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga, Fine particles such as In can be preferably exemplified, and among them, it is preferable to use fine metal particles such as Au, Ag, and Cu because they can form thin wires having low electric resistance and strong against corrosion. From the viewpoint of cost and stability, metal fine particles containing Ag are most preferable. The average particle diameter of these metal fine particles is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm. The average particle diameter is a volume average particle diameter, and can be measured with a Zetasizer 1000HS manufactured by Malvern.

  It is also preferable to use carbon fine particles as the conductive fine particles. Preferable examples of the carbon fine particles include graphite fine particles, carbon nanotubes, fullerenes and the like.

  Although it does not specifically limit as a conductive polymer, (pi) conjugated system conductive polymer can be mentioned preferably. Examples of the π-conjugated conductive polymer include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, polyparaphenylene vinylenes, polyparaphenylene sulfide. Chain conductive polymers such as polyazenes, polyazulenes, polyisothianaphthenes, and polythiazyl compounds can be used. Among these, polythiophenes and polyanilines are preferable in that high conductivity is obtained, and polyethylenedioxythiophene is most preferable.

  More preferably, the conductive polymer comprises the above-described π-conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion.

  A commercially available material can also be preferably used for the conductive polymer. For example, a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is called “CLEVIOS series” from HCStarck, “PEDOT-PASS483095”, “PEDOT-PASS560598” from Aldrich, Commercially available from Nagase Chemtex as the “Denatron Series”. Polyaniline is commercially available from Nissan Chemical Company as the “ORMECON series”.

  As a liquid which contains a conductive material in order to form the line-shaped liquid 6 described above, for example, one kind or a combination of two or more kinds such as water and an organic solvent can be used. The organic solvent is not particularly limited. For example, alcohols such as 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol, Examples include ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

  The liquid may contain various additives such as a surfactant. By using a surfactant, for example, when forming a line-shaped liquid on a substrate using an inkjet head, it becomes possible to stabilize the discharge by adjusting the surface tension and the like. . The surfactant is not particularly limited, but a silicon surfactant or the like can be used. Silicon-based surfactants are those in which the side chain or terminal of dimethylpolysiloxane is polyether-modified, such as “KF-351A”, “KF-642” manufactured by Shin-Etsu Chemical, and “BYK347” manufactured by Big Chemie. “BYK348” and the like are commercially available.

  The base material 11 is not particularly limited. For example, glass, plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metal (copper, nickel, aluminum, iron, etc. or an alloy) And ceramics, and the like. These may be used alone or in a bonded state. Among these, plastic is preferable, and polyethylene terephthalate, polyolefin such as polyethylene and polypropylene, and the like are preferable. The base material 11 is preferably a transparent base material from the viewpoint of remarkably exhibiting the effects of the present invention.

  In the above description, the case where the conductive pattern is constituted by the mesh-like conductive film and the wiring is mainly shown. However, the present invention is not limited to this, and various conductive patterns can be electroplated. In particular, the effect of the present invention becomes remarkable when a low resistance portion that is relatively easy to be plated and a high resistance portion that is relatively difficult to be plated are present on the material to be plated.

  As described above, the present invention has been described mainly by taking the case of manufacturing a touch panel sensor as an example. However, the present invention is not limited to this, and can be used for various applications as long as the material to be plated is subjected to electrolytic plating.

  Hereinafter, another embodiment of the present invention will be described with reference to FIG. 1 again.

  In this aspect, as a plurality of units constituting the conductive pattern, a unit arranged in a viewing area (for example, the product surface) in the final product and a unit arranged in a non-viewing area (for example, inside the apparatus) are conveyed in the transport direction α. Are arranged alternately.

  When plating the unit arranged in the viewing region, the anode 3a upstream in the transport direction α is adjusted to a constant voltage, and the anode 3b downstream in the transport direction α is adjusted to a constant current. While reducing the total electrical resistance of the mesh-like conductive film, it is possible to suppress an increase in the line width of the conductive thin wires constituting the mesh-like conductive film. In this way, it is possible to achieve both low resistance and low visibility of the units arranged in the visual recognition area.

  On the other hand, when plating is performed on the unit arranged in the non-visible region, the anode 3a upstream in the transport direction α is adjusted to a constant voltage, and the anode 3b downstream in the transport direction α also has the same voltage value as the anode 3a. By adjusting to a constant voltage, the total of the electrical resistance of the wiring and the meshed conductive film can be significantly reduced. Since plating is performed on the non-visible region, lowering the resistance can be prioritized over low visibility. The same effect is also obtained when the anode 3a upstream in the transport direction is adjusted to a constant current, and the anode 3b downstream in the transport direction is also adjusted to a constant current having the same current value as the anode 3a.

  As shown in this embodiment, the application conditions of the plurality of anodes 3a and 3b may be the same as a result of independently adjusting the plurality of anodes 3a and 3b. By independently adjusting the plurality of anodes 3a and 3b, various plating patterns can be freely plated to satisfy various requirements.

  As described above, in the present embodiment, the base material having the viewing area and the non-viewing area has been described. However, the non-viewing area is not necessarily limited to the area that is not normally visually observed, such as the inside of the product, and has high low visibility. It may be an area that is not required. In this embodiment, the conductive pattern having the wiring and the mesh-like conductive film is described. However, the conductive pattern is limited to the wiring pattern and the mesh-like conductive film as long as the conductive pattern has a plurality of portions having different electric resistances. Not.

  In the above description, the configuration described for one embodiment can be applied to other embodiments as appropriate.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
1. Production of material to be plated A material 1 to be plated similar to that shown in FIG. 2 was produced by the following method.

(1) Formation of mesh-like conductive film A mesh-like conductive film 14 was formed on the long sheet substrate 11 made of polyethylene terephthalate in the same manner as the example shown in FIG.

  Specifically, a plurality of line-shaped liquids 6 having a line width of 200 μm were formed on the substrate 11 by an ink jet method using an aqueous ink containing silver nanoparticles. Each line-shaped liquid 6 was formed in a direction inclined with respect to the longitudinal direction of the substrate 11. When these line-shaped liquids 6 were dried, silver nanoparticles were selectively deposited on both edges along the length direction of the line-shaped liquid 6. As a result, parallel lines composed of conductive thin wires 15 having a line width of 6 μm and parallel to each other were formed from the respective line-like liquids 6.

  Next, a plurality of further line-shaped liquids 6 are formed by the same method as described above so as to intersect with the formed conductive thin wires 15, and each line-shaped liquid 6 has a line width of 6 μm parallel to each other in the same manner as described above. Parallel lines composed of the conductive thin wires 15 were formed.

  In this manner, the mesh-like conductive film 14 was formed by crossing the plurality of conductive thin wires 15 with each other. Here, as shown in FIG. 2, a plurality of strip-like (also referred to as strip-like) mesh-like conductive films 14 are formed.

  Further, the auxiliary conductive portion 17 shown in FIG. 2 was formed of a mesh-like conductive film by the same method as described above.

(2) Formation of wiring A plurality of wirings 16 having a line width of 60 μm were formed on the base material 11 on which the mesh-like conductive film 14 was formed by an inkjet method. Each wiring 16 was formed so that one end was connected to the mesh-like conductive film 14 and the other end was connected to the auxiliary conductive portion 17 as shown in FIG.

  In forming the wiring 16, selective deposition of the conductive material during drying of the ink was suppressed, and the line width (60 μm) of the ink applied in a line shape was set to the line width of the wiring 16 as it was. .

  As described above, the conductive pattern 12 was formed on the substrate 11, and the material to be plated 1 was obtained.

2. Electrolytic plating Using the same electroplating apparatus as shown in FIG. 1, the material to be plated 1 was electroplated under the following plating conditions. The plating metal was copper, and copper plates were used for the anodes 3a and 3b. The anodes 3a and 3b are connected to an independent control circuit and are provided so as to be independently adjustable. In the following tests 1 to 6, the anodes 3a and 3b are independently adjusted to perform electrolytic plating.

<Plating conditions for Test 1>
The anode 3a disposed on the upstream side in the conveyance direction α of the material to be plated 1 was independently adjusted to a constant voltage of 10V, and the anode 3b disposed on the downstream side was independently adjusted to a constant current of 0.2A.

<Plating conditions for test 2>
The anode 3a disposed on the upstream side in the conveying direction α of the material to be plated 1 was independently adjusted to a constant current of 0.1A, and the anode 3b disposed on the downstream side was independently adjusted to a constant current of 0.2A.

<Plating conditions for Test 3>
The anode 3a disposed on the upstream side in the conveying direction α of the material to be plated 1 was independently adjusted to a constant voltage of 10V, and the anode 3b disposed on the downstream side was independently adjusted to a constant voltage of 2V.

<Plating conditions for Test 4>
The anode 3a arranged on the upstream side in the conveying direction α of the material to be plated 1 was independently adjusted to a constant current of 0.2A, and the anode 3b arranged on the downstream side was independently adjusted to a constant current of 0.2A.

<Plating conditions for test 5>
The anode 3a disposed on the upstream side in the conveying direction α of the material to be plated 1 was independently adjusted to a constant voltage of 10V, and the anode 3b disposed on the downstream side was independently adjusted to a constant voltage of 10V.

<Plating conditions for test 6>
The anode 3a arranged on the upstream side in the conveying direction α of the material to be plated 1 was independently adjusted to a constant current of 0.1A, and the anode 3b arranged on the downstream side was independently adjusted to a constant current of 0.1A.

3. Evaluation Method (1) Measurement of Electric Resistance In Tests 1 to 6, the electric resistance of the wiring after electrolytic plating and the mesh-like conductive film was measured.
The electrical resistance of the wiring is a value obtained by measuring the electrical resistance (Ω) between both electrodes by using “CD770” manufactured by Sanwa Electric Instruments Co., Ltd., with measurement electrodes arranged at intervals of 5 cm along the length direction of the wiring. It is.
The electrical resistance of the mesh-like conductive film is determined by arranging measurement electrodes having a length of 5 cm on the mesh-like conductive film at intervals of 5 cm, and using “CD770” manufactured by Sanwa Electric Instruments Co., Ltd. Ω).

(2) Measurement of line width of conductive thin wire In Tests 1 to 6, the line width of the conductive thin wire constituting the mesh-like conductive film was measured by observation with a microscope.

  The above results are shown in Table 1.

<Evaluation>
From Table 1, it can be seen that various electrolytic plating can be performed by independently adjusting the plurality of anodes 3a and 3b.

  In particular, when plating the conductive pattern used in this example, from the viewpoint of ensuring low resistance and low visibility, the electrical condition of the wiring can be changed by varying the application conditions as in Tests 1-3. The total of the resistance and the electrical resistance of the mesh-like conductive film can be reduced to 180Ω or less, and the line width of the conductive fine wire constituting the mesh-like conductive film of the conductive fine wire is 8 μm or less, and the low visibility of the mesh-like conductive film It can be seen that can be maintained well.

1: Material to be plated 11: Long sheet base material 12: Conductive pattern 13: Unit 14: Mesh-like conductive film 15: Conductive thin wire 16: Wiring 17: Auxiliary conductive part 2: Plating bath 3a-3d, 3a ′ -3d ': anode 4: cathode roll 5: transport roll 6: line-shaped liquid

Claims (9)

An electrolytic plating method for electrolytic plating in a plating bath while conveying a material to be plated having a conductive pattern on a long sheet substrate,
The conductive pattern has a plurality of portions having different electric resistances,
A method of electroplating, wherein a plurality of anodes are disposed in one plating bath, and electroplating is performed by independently adjusting application conditions to the plurality of anodes.   The electrolytic plating method according to claim 1, wherein at least one of the anodes is adjusted to a constant voltage.   3. The electrolytic plating method according to claim 2, wherein at least one of the anodes is adjusted to a constant voltage, and at least one of the anodes is adjusted to a constant current.   4. The electrolytic plating method according to claim 3, wherein the anode adjusted to a constant voltage is arranged upstream of the anode adjusted to a constant current in the conveying direction of the material to be plated.   The distance between at least one of the anodes adjusted to a constant voltage and the material to be plated is arranged shorter than the distance between the other anodes and the material to be plated. The electrolytic plating method described in 1.   The material to be plated is transported from the cathode roll in the air to the material to be plated which is not plated in the plating bath while the material to be plated is conveyed over at least the air cathode roll. The electrolytic plating method according to claim 1, wherein the electroplating is performed by feeding power in the opposite direction to the above.   The electroplating method according to any one of claims 1 to 6, wherein an electric resistance of the conductive pattern on the long sheet base material is different in a longitudinal direction of the long sheet base material.   2. The electrolytic plating method according to claim 1, wherein application conditions to the plurality of anodes are independently adjusted based on positional information of the material to be plated.   The electrolytic plating method according to claim 1 or 8, wherein the application conditions to the plurality of anodes are independently adjusted by a predetermined program.

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