JPWO2015115503A1 - Conductive pattern, substrate with conductive pattern, method for manufacturing substrate with conductive pattern, structure having conductive pattern on surface, and method for manufacturing the structure - Google Patents

Abstract

The present invention can reduce the visibility of the conductive thin wire, can reduce the resistance value, can improve the adhesion between the substrate and the conductive pattern, can suppress the fluctuation of the resistance value even when the substrate is bent, Further, a conductive pattern capable of imparting durability such as heat and humidity resistance, a substrate with a conductive pattern, a method for producing a substrate with a conductive pattern, a structure having a conductive pattern on the surface, and a method for producing the structure The pattern is composed of conductive thin wires 2 having a line width of less than 10 μm, and at least a part of the thin wires has a multilayer structure, and the multilayer structure is composed of conductive particles, conductive fillers, and conductive wires. A first layer 21 having a thickness of less than 500 nm containing one or more selected conductive materials, and a second layer 22 having a thickness greater than that of the first layer 21 and containing metal as a main component. It is characterized by.

Description

  The present invention relates to a conductive pattern, a substrate with a conductive pattern, a method for manufacturing a substrate with a conductive pattern, a structure having a conductive pattern on a surface, and a method for manufacturing the structure, and more particularly, a conductive pattern. The present invention relates to a conductive pattern composed of conductive thin wires having a line width of less than 10 μm, a substrate with a conductive pattern, a method for manufacturing a substrate with a conductive pattern, a structure having a conductive pattern on the surface, and a method for manufacturing the structure.

  The printing method is suitable for large-area and continuous production (for example, roll-to-roll), and has the merit of greatly reducing the production cost. In recent years, it has been used for manufacturing electronic components. Attempts have been made to try.

  In Patent Document 1, a circuit pattern is drawn with a metal fine particle ink using an inkjet apparatus, and then the substrate or the substrate is treated with heat or light to decompose and volatilize a polymer or a surfactant contained in the circuit pattern. It is described that a conductor pattern having a thickness of 5 mm is further plated.

  Patent Document 2 describes that a Pd circuit having a wiring of 7 μm is formed, subjected to pressure treatment, and then subjected to copper plating.

JP 2002-134878 A JP 2003-306792 A

  However, the techniques disclosed in Patent Documents 1 and 2 cannot sufficiently satisfy the following requirements (1) to (5).

(1) Decreasing the visibility of the conductive fine wires constituting the conductive pattern.
For example, when using a base material provided with a conductive pattern as a transparent electrode for a display or the like, it is required to reduce the visibility of the conductive thin wire.

(2) Lowering the resistance value of the conductive pattern by lowering the resistance value of the conductive thin wire.
In a conductive thin wire having a line width of less than 10 μm from the viewpoint of reducing visibility, a resistance value is required to be lowered in order to exhibit sufficient conductivity.

(3) To improve the adhesion between the substrate and the conductive pattern.
For example, when realizing a flexible display, it is required to improve the adhesion between the substrate and the conductive pattern in order to stably hold the conductive pattern.

(4) To make flexible by suppressing the fluctuation of the resistance value when the substrate with the conductive pattern is bent.

(5) To provide durability such as heat and humidity resistance.

  Therefore, the object of the present invention is to reduce the visibility of the conductive thin wires, to reduce the resistance value, to improve the adhesion between the substrate and the conductive pattern, and to change the resistance value even when the substrate is bent. Conductive pattern capable of suppressing heat resistance and further imparting durability such as heat and humidity resistance, a substrate with a conductive pattern, a method for producing a substrate with a conductive pattern, a structure having a conductive pattern on the surface, and a structure of the structure It is to provide a manufacturing method.

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

  The above problems are solved by the following inventions.

1.
It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. A conductive pattern comprising a second layer containing metal as a main component.

2.
2. The conductive pattern according to 1, wherein the first layer and the second layer have different film densities.

3.
3. The conductive pattern according to 1 or 2, wherein the surface of the conductive thin wire has an arithmetic average roughness Ra of 200 nm or more and less than 2000 nm.

4).
4. The conductive pattern according to claim 1, wherein the first layer has silver or copper as a main component, and the second layer has copper as a main component.

5.
5. The conductive pattern according to any one of 1 to 4, further including a third layer on the opposite side of the second layer to the first layer.

6).
On the base material subjected to the surface treatment, a pattern made of conductive thin wires having a line width of less than 10 μm is provided,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. The base material with an electroconductive pattern which uses as a component the 2nd layer which has a metal as a main component.

7).
7. The substrate with a conductive pattern according to 6, wherein the surface treatment is a treatment for increasing the surface energy of the substrate.

8).
8. The substrate having a conductive pattern according to 6 or 7, wherein the surface treatment is a treatment for forming a resin layer on the surface of the substrate.

9.
9. The substrate with a conductive pattern according to any one of 6 to 8, wherein a pattern composed of conductive thin wires having a line width of less than 10 μm is provided on both surfaces of the substrate subjected to surface treatment on both surfaces.

10.
It is a manufacturing method of the base material with a conductive pattern in any one of said 6-9,
The forming process of the first layer includes a printing process, and the printing process forms a line segment using an ink having a conductive material concentration of less than 5%, and then controls the drying process of the ink, and the line width of the line segment The manufacturing method of the base material with a conductive pattern including the process of selectively depositing a conductive material on the direction both ends.

11.
11. The method for producing a substrate with a conductive pattern as described in 10 above, wherein the surface tension of the ink is less than 50 mN / m, and the contact angle of the ink with respect to the substrate is in the range of 10 ° to 50 °.

12
12. The method for producing a substrate with a conductive pattern according to 10 or 11, wherein an inkjet method is used for forming the line segment in the printing process.

13.
13. The method for producing a substrate with a conductive pattern according to 12 above, wherein the line segment is formed by printing a plurality of times from a plurality of directions on the substrate using an inkjet method.

14
As the ink drying process, one or more selected from a process of drying the substrate during printing, a process of heating after printing, a process of blowing air after printing, and a process of irradiating light after printing are used in combination. The manufacturing method of the base material with a conductive pattern in any one of 10-13.

15.
The conductive pattern according to any one of 10 to 14, wherein the resistance is reduced by a process selected from heat treatment, chemical treatment, and light (irradiation) treatment as a subsequent step of the process of selectively depositing the conductive material. A manufacturing method of a substrate with a mark.

16.
The method for producing a substrate with a conductive pattern according to any one of 10 to 15, which includes an electrochemical process as the step of forming the second layer.

17.
17. The method for producing a substrate with a conductive pattern according to 16, wherein the electrochemical process is one of electroless plating and electrolytic plating or a combination of both.

18.
The method for producing a substrate with a conductive pattern according to any one of 10 to 17, wherein a third layer is formed on the second layer.

19.
19. The method for producing a substrate with a conductive pattern according to any one of 10 to 18, wherein a current collecting wire is formed so as to be in contact with at least a part of the conductive pattern.

20.
A structure having a conductive pattern on the surface,
The conductive pattern is
It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. The structure which has the 2nd layer which has a metal as a main component, and a component.

21.
A manufacturing method of a structure for manufacturing the structure according to the above 20,
It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. Using a base material with a conductive pattern provided on the surface treated with a conductive pattern comprising a second layer containing a metal as a main component and a component,
A structure for manufacturing a structure having a conductive pattern on its surface by bonding the substrate with a conductive pattern to the structure surface or transferring a conductive pattern portion from the substrate with a conductive pattern. Production method.

Sectional drawing which shows an example of the electroconductive thin wire which comprises the electroconductive pattern which concerns on a 1st aspect The figure which shows an example of the change of the surface roughness by providing a 2nd layer with respect to a 1st layer The figure explaining the principle which deposits a conductive material selectively in the line width direction both ends of the line segment which consists of ink containing a conductive material Explanatory drawing explaining an example of the formation process of a 1st layer Explanatory drawing explaining the other example of the formation process of the 1st layer Explanatory drawing explaining the further another example of the formation process of the 1st layer Diagram showing examples of current collector Sectional drawing which shows the other example of the electroconductive thin wire which comprises the electroconductive pattern which concerns on a 2nd aspect. The figure which shows an example of the base material in which the conductive pattern was formed in both surfaces Explanatory drawing which shows an example of the manufacturing apparatus for manufacturing the base material with an electroconductive pattern Schematic plan view explaining the basic configuration of the first layer formation zone The figure explaining an example of the formation process of the 1st layer in the 1st layer formation zone Explanatory drawing which shows the other example of the manufacturing apparatus for manufacturing the base material with a conductive pattern Explanatory drawing which shows an example of the structure in which the electroconductive pattern was formed Explanatory drawing which shows the example of the method of forming a conductive pattern in the structure surface using a base material with a conductive pattern The figure explaining an Example The figure explaining an Example The figure explaining the testing apparatus of an Example

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of a thin conductive wire constituting the conductive pattern according to the first embodiment.

  In FIG. 1, 1 is a base material, 2 is a conductive fine wire which comprises a conductive pattern.

  The line width of the conductive thin wire 2 is less than 10 μm.

  The conductive thin wire 2 has a multilayer structure, and in the example shown in the figure, a first layer 21 and a second layer 22 are included as components of the multilayer structure.

  The first layer 21 includes a conductive material selected from conductive particles, conductive fillers, and conductive wires, and has a thickness of less than 500 nm.

  The second layer 22 is thicker than the first layer 21 and contains metal as a main component.

  The conductive pattern composed of the conductive thin wires having the specific multilayer structure can reduce the visibility of the conductive thin wires, can reduce the resistance value, can improve the adhesion between the substrate and the conductive pattern, It is possible to suppress fluctuations in the resistance value even during bending, and to provide durability such as resistance to heat and humidity. Therefore, for example, it has excellent characteristics suitable for use as a transparent electrode film or the like provided on a flexible substrate.

  The line width of the conductive thin wire 2 is set to be less than 10 μm, preferably 3 to 8 μm. When the line width is in the range of 3 to 8 μm, disconnection of the conductive thin wire 2 can be more suitably prevented, and visibility can also be suitably reduced. It is also preferable that the line width is in the range of 3 μm or more, less than 7 μm, and further less than 5 μm. An example of a preferable method for providing such a thin line width will be described in detail later.

  The conductive material contained in the first layer 21 of the conductive thin wire 2 may be any combination of one or more selected from conductive particles, conductive fillers, and conductive wires, and is particularly limited. Although not intended, for example, metal nanoparticles having a particle diameter of less than 100 nm (for example, silver nanoparticles, copper nanoparticles, etc.), conductive fillers such as silver powder and copper powder, or silver nanowires and copper nanowires Preferred examples thereof include conductive nanowires. In addition, a conductive carbon material (eg, graphite, carbon nanotube, graphene, or the like) can be used.

  The first layer 21 is particularly preferably composed mainly of silver and copper. Conversely, palladium and platinum are not preferable because the number of steps is increased, for example, a separate reduction step is required.

  Although the film thickness of the 1st layer 21 will not be specifically limited if it is less than 500 nm, It is more preferable that it is the range of 30 nm-300 nm.

  Although the metal contained as a main component in the 2nd layer 22 of the electroconductive thin wire 2 is not specifically limited, The 1 type, or 2 or more types of combination chosen from silver, copper, nickel, etc. can be illustrated preferably. In particular, the second layer is preferably composed mainly of copper.

  Although the film thickness of the 2nd layer 22 will not be specifically limited if it is thicker than the film thickness of a 1st layer, It is preferable that it is the range of 600 nm-5 micrometers. The film thickness of the second layer 22 is a thickness measured from the surface of the first layer.

  Regarding the film thickness ratio between the first layer 21 and the second layer 22, the film thickness of the second layer 22 is preferably 5 times or more, more preferably 10 times or more of the film thickness of the first layer 21. .

  The film density of the first layer 21 and the film density of the second layer 22 are preferably different from each other.

In particular, the film density of the second layer 22 is preferably higher than the film density of the first layer 21. At this time, the film density difference is particularly preferably 1 g / cm ³ or more.

For example, the film density of the first layer ^21, in the range of ^{5g / cm 3 ~8g / cm 3} , it is preferable that the film density of the second layer 22 in the range of ^{6g / cm 3 ~9g / cm 3} . It is most preferable that the above film density difference is formed within these ranges.

  The film density can be measured by using an X-ray reflectivity method.

  The surface of the conductive thin wire 2 constituting the conductive pattern preferably has a large surface roughness. For example, the arithmetic average roughness Ra is preferably 200 nm or more and less than 2000 nm, and may be in the range of 300 nm to 1200 nm. More preferred. The arithmetic average roughness Ra can be measured using a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100. Thereby, the effect which can further reduce the visibility of the electroconductive thin wire 2 is acquired.

  For example, it is preferable that the surface roughness after forming the second layer 22 is larger than the surface roughness of the first layer 21 from the viewpoint of further reducing the visibility of the conductive thin wire 2.

  FIG. 2 is a diagram illustrating an example of a change in surface roughness caused by providing the second layer 22 with respect to the first layer 21. 2A is an electron micrograph of the surface of the first layer 21 where the second layer is not yet provided. FIG. 2B is a diagram after the second layer 22 is provided on the first layer 21. FIG. 2 is an electron micrograph of the surface of the conductive thin wire 2 of FIG.

  As shown in the figure, by providing the second layer 22 with respect to the first layer 21, irregularities are formed on the surface, and the surface roughness can be increased.

  The substrate 1 is not particularly limited, and plastic, glass, metal (for example, copper, nickel, aluminum, iron, etc., or an alloy), ceramic, or the like can be used alone or in combination. In particular, plastics are preferable from the viewpoint of flexibility, and among them, polyethylene, polypropylene, acrylic, polyester, polyamide, and the like are preferable. In particular, polypropylene such as polyethylene terephthalate (also referred to as PET) and polybutylene terephthalate (also referred to as PBT) is suitable.

  The surface of the substrate 1 on which the conductive thin wires 2 are formed may be smooth or rough.

  In the case of a rough surface, the maximum height Ry is preferably less than 5 mm, and more preferably in the range of 0.3 mm to 2 mm. The maximum height Ry can be measured using a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100.

  The specific surface state of the rough surface is not particularly limited, but in particular, it is optically reflective to a specific wavelength, such as a shape in which irregularities are regularly repeated with a period and a shape in which conical pillar structures are continuous. It is preferable to use a rough surface base material having a function of controlling absorption. When the conductive pattern of the present invention is formed on such a substrate, it is preferable because it can have both a conductive function and an optical function.

  The substrate 1 is preferably surface-treated in advance. Preferred examples of the surface treatment include solvent cleaning, surfactant aqueous solution cleaning, UV ozone cleaning, plasma processing, and resin layer formation.

  When the resin layer is formed as the surface treatment, a resin substituted with a hydroxyl group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a polyoxyethylene group, or the like is preferable. An acrylic resin, a polyester resin, a polyamide resin, a polyurethane Resins and the like can be preferably used.

  The weight average molecular weight of the resin is preferably 5000 or more and 500,000 or less. The resin may have a cross-linked structure.

  The thickness of the resin layer is preferably in the range of 50 nm to 5 μm.

  The method for forming the resin layer is not particularly limited, but is preferably formed by a printing method, an inkjet method, a dip method, or the like.

  The surface treatment is preferably a treatment for increasing the surface energy of the substrate 1. It is preferable to increase the surface energy of the substrate 1 by 5 mN / m or more by surface treatment.

  As a result of the surface treatment, the surface energy of the substrate 1 is preferably 50 mN / m or more. In particular, the surface energy of the substrate 1 is preferably set in a range of 50 mN / m or more and less than 70 mN / m.

  The surface treatment may be performed on the entire substrate 1 or may be partially performed on a portion including a region where the conductive thin wire is formed.

  Further, for example, when the conductive pattern portion formed on the base material 1 is transferred to a structure or the like as will be described later, an appropriate peeling is provided between the base material 1 and the conductive pattern portion. It is also preferable to impart a property (hereinafter also referred to as “easy peelability”). In this case, as a treatment for imparting easy peelability to the substrate 1, a silicone resin layer is provided, and the upper layer is treated as the surface treatment of the present invention. It is preferable to provide a resin layer or the like. In this case, the silicone resin layer preferably has a thickness of 10 nm to 10 μm, and a silicone resin such as a solvent type, a solventless type, or an emulsion type can be used.

  Next, the manufacturing method for manufacturing the base material with an electroconductive pattern provided with the electroconductive pattern demonstrated above on the base material 1 is demonstrated.

  The substrate 1 can be subjected to the surface treatment described above in advance.

  When forming the 1st layer 21 on the base material 1, it is preferable to use a printing process, for example. The printing process is not particularly limited as long as the conductive material is applied on the substrate 1 as ink.

  As a particularly preferable aspect, the printing process forms a line segment using an ink having a conductive material concentration of less than 5%, and then controls the drying process of the ink to selectively deposit the conductive material on both ends in the line width direction of the line segment. It is preferable to include the process to make this process, and this point is demonstrated in detail below.

  FIG. 3 is a diagram for explaining the principle of selectively depositing a conductive material on both ends in the line width direction of a line segment made of ink containing a conductive material.

  In the process of drying a line segment (hereinafter sometimes referred to as a line-like liquid) 20 made of a liquid containing a conductive material on the substrate 1, the drying speed is higher at the edge than at the center of the line-like liquid 20. Since it tends to be faster (FIG. 3A), local deposition of the conductive material is promoted at the edge of the line-shaped liquid 20 (FIG. 3B). Thereby, fixation of the contact line (edge part) of the line-shaped liquid 20 occurs, and shrinkage of the line-shaped liquid 20 in the substrate surface direction accompanying subsequent drying is suppressed. Due to this effect, the liquid in the line-shaped liquid 20 forms convection from the center to the edge so as to compensate for the liquid lost by drying at the edge (FIG. 3C). By this convection, the conductive material in the line-shaped liquid 20 is carried to both ends in the line width direction, and further deposition is promoted. The first layer 21 is formed by the conductive material thus deposited (FIG. 3D).

  Since the first layer 21 generated by the selective deposition of the conductive material can be made thinner than the first line segment, the conductive pattern can be made thinner.

  The ink used in the printing process has a conductive material concentration of less than 5% and preferably less than 1%.

  The ink can be used as a solvent or a dispersion medium of the conductive material, and one or two or more of water, an organic solvent, and the like can be used in combination, but an aqueous ink containing water is preferable. It is also preferable to include a surfactant in the ink.

  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 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 dimethylpolysiloxy acid is polyether-modified. For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. ing.

  The surface tension of the ink is preferably less than 50 mN / m, and more preferably less than 40 mN / m. Further, the contact angle of the ink with respect to the substrate 1 is preferably 10 ° to 50 °. The surface tension can be controlled by a solvent, a surfactant or the like. The same control can be performed for the adjustment of the contact angle, but it can also be performed by setting the surface energy of the substrate 1.

  When a line segment is formed on the substrate 1 using ink, an ink jet method can be particularly preferably used. As the ink droplet discharge mechanism of the ink jet head, a thermal method, a piezo method, a continuous method, or the like can be preferably exemplified. The amount of droplets ejected by one droplet ejection from one nozzle of the inkjet head by the inkjet method is preferably in the range of 1 pl to 200 pl, more preferably in the range of 1 pl to 100 pl.

  In the case of using the inkjet method, it is also preferable to print the substrate 1 multiple times from a plurality of directions. This aspect will be described with reference to the examples of FIGS. 4, 5, and 6.

  FIG. 4 is an explanatory diagram for explaining an example of the formation process of the first layer 21.

  As shown in FIG. 4A, first, the inkjet head is scanned a plurality of times along the longitudinal direction of the substrate 1 to form a striped first layer along the longitudinal direction. On the other hand, as shown in FIG. 4B, the inkjet head is scanned a plurality of times along the short direction of the substrate 1 to form a stripe-shaped first layer along the short direction. . In this manner, a lattice-shaped first layer in which the stripes in the longitudinal direction intersect with the stripes in the short direction can be formed.

  FIG. 5 is an explanatory diagram for explaining another example of the formation process of the first layer 21.

  As shown in FIG. 5A, first, the inkjet head is scanned a plurality of times along a direction inclined at a predetermined angle (45 ° in this case) from the longitudinal direction of the base material 1 to form a stripe shape along the direction. The first layer is formed, and then the formation region is further inclined at another predetermined angle (here, −45 °) from the longitudinal direction of the substrate 1 as shown in FIG. 5B. The inkjet head is scanned a plurality of times along the direction to form a striped first layer along the direction. In this way, a grid-like first layer can be formed by oblique lines inclined from the longitudinal direction of the substrate 1.

  FIG. 6 is an explanatory diagram for explaining still another example of the formation process of the first layer 21.

  In this example, as in the example of FIG. 4, the inkjet head is scanned a plurality of times along the longitudinal direction of the substrate 1 to form the first layer (FIG. 6A), and further along the short direction. The ink jet head is scanned a plurality of times to form the first layer (FIG. 6B). By controlling the ejection of ink from the ink jet head, a grid-like first layer is formed by wavy lines. ing.

  For example, in the case where the substrate 1 on which the conductive pattern is formed is overlapped with another member to form a device, interference fringes are generated between the conductive pattern and the pattern provided on the other member. However, for example, as in the example of FIG. 5, the pattern is inclined from the longitudinal direction (or short direction) of the substrate, or the lines constituting the pattern are made wavy as in the example of FIG. By doing so, it is possible to obtain the effect of suitably preventing the generation of interference fringes.

  The drying process of the ink applied on the substrate 1 is not particularly limited. For example, the process of drying the substrate 1 during printing, the process of heating after printing, the process of blowing air after printing, and It is preferable to use a combination of one or more selected from the processes of light irradiation after printing.

  In particular, it is preferable to dry the substrate 1 during printing. For example, it is preferable to heat the substrate 1 so that the temperature of the substrate 1 is 40 ° C to 80 ° C. Even when the process of heating after printing is performed, it is preferable to heat the substrate 1 in such a temperature range.

  The drying process after printing is preferably performed immediately after printing.

  The light used for the light irradiation is not particularly limited as long as it can accelerate the drying of the ink, but an infrared ray or the like can be preferably exemplified.

  It is also preferable to subject the first layer 21 to a resistance reduction treatment as a post-treatment for the process of selectively depositing a conductive material. For example, the resistance of the first layer 21 can be reduced by performing a process selected from a heat process, a chemical process, and a light irradiation process.

  Although the temperature of heat processing is not specifically limited, The temperature of the range of 80 to 300 degreeC is applicable. When the substrate 1 is a film, it is preferable to apply a temperature in the range of 80 ° C to 180 ° C.

  As the chemical treatment, for example, a treatment for removing an organic substance or the like in the conductive material can be preferably exemplified, and a method of washing with an acidic or basic washing aqueous solution, a method of washing with a solvent or a solvent aqueous solution, and the like can be used.

  For the light irradiation treatment, for example, flash sintering or IR irradiation can be used.

  The first layer 21 can be subjected to a resistance reduction process in which one or more of the processes described above are combined.

  Such resistance reduction processing may be performed during printing. For example, when a pattern is completed by a plurality of scans by the ink jet method, the resistance reduction process may be performed in the middle of the process once, or divided into a plurality of times. In particular, as described above, when printing a plurality of times from a plurality of directions on the base material, it is preferable to perform a resistance reduction process in the middle.

  In forming the second layer 22, it is preferable to use an electrochemical process. As an electrochemical process, it is preferable to use either or both of an electroless plating method and an electrolytic plating method.

  The electrolytic plating method refers to a method of depositing a metal by electrolysis on a conductive object using a solution in which metal ions to be deposited as a plating are dissolved. Here, the second layer can be formed using the first layer 21 as the conductive object.

  The electroless plating method refers to a method in which a metal is deposited on a catalyst by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved. Here, the second layer can be formed using the first layer 21 as a catalyst.

  It is also preferable that a current collector (hereinafter sometimes referred to as an extraction electrode or an extraction wiring) is formed so as to be connected to at least a part of the conductive pattern.

  FIG. 7 is a diagram illustrating an example of forming a current collecting line.

  In this example, four conductive patterns 200 are provided on the substrate 1.

  The current collector 3 is provided on the substrate 1 so as to surround each conductive pattern 200, and is connected to a part of the conductive thin wire 2 constituting the conductive pattern 200.

  The current collecting wire 3 is further connected to the wiring 4, and the wiring 4 extends to the end of the substrate 1.

  The line width of the current collector 3 is larger than the line width of the conductive thin wires 2 constituting the conductive pattern 200, preferably 15 μm or more, more preferably 50 μm or more, and most preferably 100 μm or more. The upper limit of the line width is not particularly limited, but is preferably less than 5 mm. In the current collector 3, the line width of the portion directly coupled to the conductive fine wire 2 constituting the conductive pattern 200 is preferably 15 μm or more and less than 100 μm.

  In the above example, the example in which the current collecting line 3 is provided along the four sides of the conductive pattern 200 having a rectangular shape as a whole has been shown. For example, the current collecting line 3 is provided along two opposing sides, or on one side. It is also preferable to provide it along. Further, it is not necessarily provided along the side, and it is only necessary to be connected to at least a part of the conductive thin wire 2 constituting the conductive pattern 200.

  When the second layer 22 of the conductive thin wire 2 is formed by an electrochemical process, the current collector 3 is connected to at least a part of the first layer 21 before the second layer 22 is formed. It is preferable to form them in the same manner. At this time, the current collector 3 may be formed before the formation of the first layer 21 or may be formed after the formation of the first layer 21. Since the first layer 21 can be stably energized via the current collector 3, the second layer 22 can be stably formed by an electrochemical process, particularly by electrolytic plating.

  In addition, the current collector 3 can ensure stable energization of the conductive pattern 200 even in the finished product.

  FIG. 8 is a cross-sectional view showing another example of the conductive fine wire constituting the conductive pattern according to the second embodiment.

  In the second aspect, the conductive thin wire 2 is a first layer of the second layer 22 in addition to the first layer 21 and the second layer 22 described above as a component of a multilayer structure constituting at least a part thereof. A third layer 23 is further provided on the side opposite to the side 21.

  The material of the third layer 23 is not particularly limited, but in terms of causing the third layer 23 to function as a protective layer for protecting the conductive pattern, a corrosion-resistant metal such as Ni or Cr, or an organic material. It is preferable to configure with a film.

  In manufacturing the conductive pattern according to the second aspect, the first layer 21 and the second layer 22 of the conductive thin wire 2 are formed using the method described as the method for manufacturing the conductive pattern according to the first aspect. The conductive pattern according to the second mode can be manufactured by forming the third layer 23 on the second layer 22.

  The method for forming the third layer 23 is not particularly limited, but it is preferable to use an electrochemical process.

  When the third layer 23 is made of a metal such as a corrosion-resistant metal, it is preferable to use either or both of an electroless plating method and an electrolytic plating method as an electrochemical process.

  When the third layer is composed of an organic film or the like, it is preferable to use a method selected from an electrodeposition method, an electrolytic polymerization method, and the like. At this time, the third layer 23 can be formed using the first layer 21 and the second layer 22 as electrodes.

  In the above description, an example in which a conductive pattern is formed on one surface of the substrate 1 has been shown, but the present invention is not limited to this.

  It is also preferable that the conductive pattern described above is formed on both surfaces of the substrate 1.

  Both surfaces of the substrate 1 are preferably subjected to the surface treatment described above in advance prior to the formation of the conductive pattern. For the surface treatment, the same surface treatment may be applied to the front surface and the back surface of the substrate 1, or different surface treatments may be applied.

  The conductive patterns provided on the front surface and the back surface of the substrate 1 may be the same or different. Moreover, the structure of the 1st layer 21 of the electroconductive thin wire | line 2 and the 2nd layer 22 may be the same or different by the surface and a back surface. As long as the conductive pattern according to the second aspect, the configuration of the third layer 23 may be the same or different between the front surface and the back surface. The conductive pattern according to the first aspect may be formed on one surface, and the conductive pattern according to the second aspect may be formed on the other surface.

  FIG. 9 is a diagram illustrating an example of the base material 1 on both surfaces of which a conductive pattern is formed. FIG. 9A is a plan view of the front surface and FIG. 9B is a plan view of the back surface.

  As shown in FIG. 9A, a plurality of conductive patterns 200 are provided on the surface of the substrate 1. These conductive patterns 200 are lattice-like patterns formed by the conductive thin wires 2 formed by oblique lines inclined from the longitudinal direction of the substrate 1.

  These conductive patterns 200 provided on the surface have a rectangular shape (strip shape) as a whole, and their long sides are arranged along the short direction of the substrate 1.

  In addition, a current collecting line 3 is provided on these conductive patterns 200 so as to surround the conductive pattern 200 with four sides.

  On the other hand, as shown in FIG. 9B, a plurality of conductive patterns 200 are provided on the back surface of the substrate 1. These conductive patterns 200 are lattice-like patterns formed by the conductive thin wires 2 formed by oblique lines inclined from the longitudinal direction of the substrate 1.

  These conductive patterns 200 provided on the back surface have a rectangular shape (strip shape) as a whole, and their long sides are arranged along the longitudinal direction of the substrate 1.

  In addition, a current collecting line 3 is provided on these conductive patterns 200 so as to surround the conductive pattern 200 with four sides.

  The strip-shaped conductive pattern 200 provided on the front surface and extending in the short direction of the base material 1 and the strip-shaped conductive pattern 200 provided on the back surface and extending in the longitudinal direction of the base material 1 sandwich the base material 1. Are three-dimensionally crossed and arranged in a grid pattern. Such a pattern can be suitably used as an X and Y pattern in a capacitive touch sensor, for example, on a single substrate made of a film. One of the conductive pattern 200 on the front surface and the conductive pattern 200 on the back surface can be an X pattern and the other can be a Y pattern.

  Next, the present invention will be described in more detail with reference to an example of a production apparatus for producing a substrate with a conductive pattern.

  FIG. 10 is an explanatory diagram illustrating an example of a manufacturing apparatus for manufacturing a substrate with a conductive pattern.

  The illustrated manufacturing apparatus is configured to form a conductive pattern on a substrate by a roll to roll method.

  5 is a wound body in which the substrate is wound, 6 is a first layer forming zone, 7 is a support roller, 8 is a drying zone, and 9 is a low resistance zone. 10 is a second layer forming zone, 11 is a third layer forming zone, and 12 is a wound body on which a substrate on which a pattern is formed is wound.

  A conductive pattern is formed on the base material 1 in the conveying process until the belt-like base material 1 fed out from the wound body 5 is wound around the wound body 12. In the following description, the direction from the wound body 5 toward the wound body 12 may be referred to as a conveyance direction.

  The strip-shaped base material 1 fed out from the wound body 5 is conveyed to the first layer forming zone 6 for forming the first layer 21.

  FIG. 11 is a schematic plan view illustrating the basic configuration of the first layer formation zone 6.

  As shown in FIG. 11, in this example, the first layer formation zone 6 is also provided with an ink jet head 62 for drawing the lead-out wiring 3 together with a head array 61 for forming the first layer 21. . The head array 61 can be configured by arranging a plurality of inkjet heads in an array.

  In the first layer formation zone 6, first, the lead-out wiring 3 is formed on the substrate 1 by the ink-jet head 62 for drawing the lead-out wiring.

  The region of the substrate 1 on which the lead wiring 3 is formed is transported to the drying zone 8 where it is dried.

  Then, the said area | region of the base material 1 is reversely conveyed by a fixed amount in the direction which goes to the wound body 5, and is provided to the 1st layer formation zone 6 again.

  Then, the first layer 21 is formed on the substrate 1 by the head array 61 for forming the first layer 21 provided in the first layer forming zone 6.

  FIG. 12 is a diagram for explaining an example of the formation process of the first layer 21 in the first layer formation zone 6.

  As shown in FIG. 12A, in the first printing process in the forming process, the head array 61 is moved in the direction orthogonal to the transport direction (the direction toward the right in the figure) while transporting the substrate 1 in the transport direction. Scan. Thus, by simultaneously moving the base material 1 and the head array 61, the head array 61 can be moved relative to the base material 1 in an oblique direction. In the process of this relative movement, by ejecting ink containing a conductive material from the head array 61 onto the substrate 1, a line segment inclined at a predetermined angle with respect to the transport direction of the substrate 1 can be drawn. it can. For example, by making the conveyance speed of the substrate 1 and the scanning speed of the head array 61 the same, a line segment inclined at 45 ° can be drawn. The inclination angle can be set to an arbitrary value by adjusting the scanning speed of the head array 61 and / or the conveyance speed of the substrate 1.

  Subsequently, the area | region of the base material 1 in which the line segment was formed is conveyed to the drying zone 8, and is dried here. By controlling this drying process, the conductive material can be selectively deposited at both ends of the line width direction.

  Then, the said area | region of the base material 1 is reversely conveyed by the fixed amount in the direction which goes to the wound body 5, and is provided to the 2nd printing process in the 1st layer formation zone 6. FIG.

  As shown in FIG. 12B, in the second printing process, the head array 61 is moved in the direction perpendicular to the conveying direction while conveying the base material 1 in the conveying direction, and in the first printing process. Scan in the direction opposite to the scanning direction (the direction toward the left in the figure). In the process of this relative movement, by ejecting ink containing a conductive material from the head array 61 onto the substrate 1, a predetermined angle in the direction opposite to the first printing step with respect to the conveyance direction of the substrate 1 is obtained. It is possible to draw a line segment inclined by. For example, by making the conveyance speed of the substrate 1 and the scanning speed of the head array 61 the same, a line segment inclined at −45 ° can be drawn. In this way, as shown in the drawing, the line segment formed in the first printing process (inclination angle 45 °) and the line segment formed in the second printing process (inclination angle −45 °) are combined. It is also possible to cross at right angles.

  Subsequently, the area | region of the base material 1 in which the line segment was formed is conveyed to the drying zone 8, and is dried here. By controlling this drying process, the conductive material can be selectively deposited at both ends of the line width direction of the line segment formed in the second printing step.

  In this way, the lattice-like first layer 21 made of diagonal lines can be formed.

  The region of the base material 1 on which the first layer 21 is formed is transported to the low resistance zone 9.

  In this example, the low resistance zone 9 is provided with an oven, and the resistance reduction treatment of the first layer 21 is performed by heating the base material 1 with the oven.

  The area | region of the base material 1 in which the resistance reduction process was performed is conveyed to the 2nd layer formation zone 10. FIG.

  In this example, the second layer forming zone 10 is provided with an electrolytic plating apparatus for forming the second layer 22.

  The electrolytic plating apparatus forms, for example, a base material 1 across a plurality of transport rolls to form a transport system, and one or two or more of these transport rolls are used as external electrodes in a plating solution (plating bath). , Also referred to as an electrolytic solution). A counter electrode is provided in the plating solution.

  The second layer 22 can be formed by supplying power from the external electrode to the first layer 21 through the lead-out wiring 3 and performing electrolytic plating in a plating solution by an electrolytic plating apparatus.

  The second layer forming zone 10 is preferably provided with a washing machine for washing the region of the base material 1 after electrolytic plating with a washing liquid such as water, a drying machine for drying the washing liquid, and the like.

  In this example, the region of the base material 1 on which the second layer 22 is formed is further conveyed to the third layer forming zone 11.

  The third layer forming zone 11 is provided with an electrolytic plating apparatus for forming the third layer 23. The configuration described in the second layer formation zone 10 can be used for the basic configuration of the electrolytic plating apparatus.

  The third layer forming zone 11 is also preferably provided with a washing machine for washing the region of the substrate 1 after the electrolytic plating with a washing liquid such as water, a drying machine for drying the washing liquid, and the like.

  As described above, a conductive pattern can be formed on the substrate 1. The area | region of the base material 1 in which the electroconductive pattern was formed can be comprised so that the winding body 12 may be wound up sequentially.

  FIG. 13 is an explanatory view showing another example of a production apparatus for producing a substrate with a conductive pattern. In the figure, the same reference numerals as those in FIG. 10 can have the same configuration, and the description of FIG. 10 can be used.

  The manufacturing apparatus shown in this example can be suitably used for forming a conductive pattern on both surfaces of a base material.

  First, in the upstream line A, on the one surface (surface) of the belt-like base material 1 drawn out from the wound body 13, the treatment in the first layer forming zone 6 and the drying zone 8 is performed as in the example of FIG. 10. Thus, the first layer 21 is formed.

  The base material 1 on which the first layer 21 is formed on one surface (front surface) is wound around the wound body 14.

  When the winding is finished, the wound body 14 is replaced with the wound body 13 and set so that the front and back surfaces are reversed, and again by the processing in the first layer forming zone 6 and the drying zone 8, This time, the first layer 21 is formed on the other surface (back surface) of the substrate 1.

  In this way, the base material 1 having the first layer 21 formed on both surfaces of the base material 1 is wound around the wound body 14.

  Next, the wound body 14 is set as the wound body 15 in the downstream line B.

  In the downstream side line B, as in the example of FIG. 10, the low resistance zone 9, the second layer forming zone 10, and the third layer forming zone 11 are applied to the belt-like base material 1 drawn out from the wound body 15. Through the process, the resistance of the first layer is reduced, the second layer 22 is formed, and the third layer 23 is formed. Thereafter, the substrate 1 after each process is wound around the wound body 16.

  Since each process in the downstream line B is easy to apply to both surfaces of the substrate 1 at the same time, it is easy to configure the roll to roll in the downstream line B to be finished in one pass.

  The object on which the conductive pattern described above is formed is not limited to a two-dimensional sheet-like substrate, and can be preferably applied to a three-dimensional structure (sometimes simply referred to as a structure).

  A structure refers to an object other than a two-dimensional sheet, and is special if it includes a three-dimensional shape, such as a rectangular parallelepiped shape, a spherical shape, a cylindrical shape, a prism shape, a combination thereof, or a curve (curved surface). It is not limited.

  FIG. 14 is an explanatory diagram illustrating an example of a structure in which a conductive pattern is formed.

  In the illustrated example, the conductive pattern 200 is formed on the curved surface of the structure 100.

  The material of the structure 100 is not particularly limited, but plastics, metals, ceramics, stones, pulp, those formed from wood, rubber, composite materials thereof, and the like can be preferably exemplified.

  The conductive pattern 200 can be provided on the entire surface of the structure 100 or a part thereof.

  On the surface of the structure 100, image information (not shown) may be displayed at a specific portion where the conductive pattern is formed so that the specific portion can be identified. Image information on the surface of the structure can be provided so as to be visible through the conductive pattern when the conductive pattern is formed thereon. The image information is not particularly limited, but preferable examples include characters, symbols, and coloring patterns. These pieces of image information can guide functions such as position detection in applications such as switches, keyboards, touch panels, and sensors. The image information need not always be displayed, and may be configured to be displayed under specific conditions, for example.

  The method of manufacturing the structure 100 including the conductive pattern 200 is not particularly limited, and the conductive pattern may be directly formed on the surface of the structure 100. However, as an example of a preferable method, the conductive pattern is formed. An example of the method of manufacturing using the prepared base material (base material with conductive pattern) can be given.

  For example, using a method in which a substrate with a conductive pattern is bonded to the surface of the structure 100 or a method in which a portion of the conductive pattern 200 is transferred from the substrate with a conductive pattern to the surface of the structure 100, the surface is electrically conductive. It is preferable to manufacture the structure 100 having the pattern 200.

  FIG. 15 is an explanatory diagram illustrating an example of a method for forming the conductive pattern 200 on the surface of the structure 100 using a substrate with a conductive pattern.

  In the example of FIG. 15A, the base material 1 on which the conductive pattern 200 is formed is bonded to the structure body 100 through the adhesive layer 17 so that the conductive pattern 200 side is oriented to the structure body 100 side. They are pasted together. Reference numeral 18 denotes a resin layer provided on the substrate 1, and the conductive pattern 200 is formed on the surface of the resin layer 18 on the substrate 1. As described above, the conductive pattern 200 can be formed on the surface of the structure 100 by bonding the substrate with the conductive pattern to the surface of the structure 100.

  Further, as in the example of FIG. 15B, by further providing a step of peeling the base material 1 from the conductive pattern 200 shown in the example of FIG. The pattern 200 can be transferred. In this case, for example, an easy peeling process for facilitating peeling is performed in advance between the base material 1 and the resin layer 18 so that the base material 1 and the resin layer 18 are easily peeled off. be able to.

  Although the use of the conductive pattern of the present invention is not particularly limited, it can be suitably used as a transparent conductive film or the like.

  The use of the substrate with a conductive pattern and the structure of the present invention is not particularly limited, but can be used for various devices included in various electronic apparatuses. From the viewpoint of prominently achieving the effects of the present invention, for example, as a transparent electrode for various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, etc., or as a touch panel, a mobile phone, electronic paper, various solar cells, various electro It can be suitably used as a transparent electrode used in a luminescence light control element or the like.

  More specifically, the substrate with a conductive pattern and the structure according to the present invention are suitably used as a transparent electrode of a device. Although it does not specifically limit as a device, For example, a touch panel sensor etc. can be illustrated preferably. Moreover, although it does not specifically limit as an electronic device provided with these devices, For example, a smart phone, a tablet terminal, etc. can be illustrated preferably.

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

<Preparation of substrate>
The following base materials 1 to 4 were prepared as base materials. The base materials 1 and 2 are not subjected to surface treatment, and the base materials 3 and 4 are subjected to surface treatment.
-Substrate 1: Commercially available low thermal shrinkage PET film (thickness 120 μm) for optical use, and surface energy is 50 mN / m.
Substrate 2: A commercially available low heat shrinkage PET film (thickness 120 μm) different from the substrate 1 and having a surface energy of 42 mN / m.
-Base material 3: The base material 1 is surface-treated and the surface energy is adjusted to 60 mN / m.
-Base material 4: The base material 2 is surface-treated and the surface energy is adjusted to 60 mN / m.

<Preparation of ink>
Ink 1 (silver nanoparticle-containing ink 1)
The silver nanoparticle dispersion (Bandow Chemical SW1000) is 0.2 wt% as a solid (silver nanoparticle), 20 wt% diethylene glycol monobutyl ether, and the rest is 100 wt% with ion-exchanged water, and this is filtered through a 1 μm filter. .
The obtained permeate was designated as ink 1. The concentration of the silver nanoparticles as conductive particles did not substantially change before and after the filtration, and was 0.2 wt% in ink 1. The viscosity of the ink 1 was 2.0 mPa · s, and the surface tension was 29 mN / m.

Ink 2 (silver nanoparticle-containing ink 2)
Silver nanoparticle dispersion (Bundo Chemical SW1000) as a solid (silver nanoparticles), 0.2 wt%, 1,3-butanediol 25 wt%, surfactant (BYK348 "BYK348") 0.5 wt% The remainder was made up to 100 wt% with ion-exchanged water and filtered through a 1 μm filter.
The obtained permeate was designated as ink 2. The concentration of silver nanoparticles as conductive particles did not substantially change before and after the filtration, and was 0.2 wt% in ink 2. The viscosity of the ink 2 was 3.5 mPa · s, and the surface tension was 31 mN / m.

・ Ink 3 (ink containing copper nanoparticles)
Copper nanoparticle dispersion as solid content (copper nanoparticle) 0.2 wt%, ethylene glycol 30 wt%, surfactant ("BYK348" manufactured by Big Chemie) 0.5 wt%, the balance to 100 wt% with ion-exchanged water Finished and filtered through a 1 μm filter.
The obtained permeate was designated as Ink 3. The concentration of copper nanoparticles as conductive particles did not substantially change before and after the filtration, and was 0.2 wt% in ink 3. The viscosity of the ink 3 was 4.0 mPa · s, and the surface tension was 32 mN / m.

Ink 4 (ink containing silver powder)
Silver powder with an average particle size of 0.5 μm, 0.1 wt%, ethylene glycol 30 wt%, surfactant (“BYK348” manufactured by BYK Chemie) 0.5 wt%, and the balance is ion-exchanged water to 100 wt%, and this is a 1 μm filter. And filtered.
The obtained permeate was designated as Ink 4. The concentration of silver powder particles as conductive particles did not substantially change before and after the filtration, and was 0.1 wt% in ink 4. The viscosity of the ink 4 was 4.0 mPa · s, and the surface tension was 32 mN / m.

・ Silver nano ink for lead-out wiring Silver nano particle dispersion (SW1000 manufactured by Bando Chemical Co., Ltd.) as solid content (silver nano particles), 15 wt%, propylene glycol 20%, and the rest to 100 wt% with ion-exchanged water, 1 μm filter The obtained permeate was filtered to obtain a silver nano ink for wiring.

(Sample No. 1)
Using the apparatus shown in FIG. 10, a conductive pattern was prepared as follows on a roll-shaped substrate having a width of 300 mm.

<Formation of current collector (drawer wiring)>
First, the lead-out wiring was drawn using the lead-out wiring silver nano ink using the lead-out wiring inkjet head provided in the first layer forming zone 6.

  The ink applied on the substrate was dried by blowing air at 70 ° C. for 5 minutes in the drying zone 8.

<Formation of the first layer>
After the drying, the first layer was patterned in the first layer formation zone 6.

  In the first layer formation zone 6, as shown in FIG. 11, a head array 61 is arranged so as to be orthogonal to the substrate transport direction.

  In the head array 61, five inkjet heads ("KM1024L" manufactured by Konica Minolta Co., Ltd. (piezo method, droplet amount 42pL)) are arranged, and the print width of the entire array is 360 mm.

While transporting the base material in the base material transport direction, the head array 61 is simultaneously scanned in the right direction, the conductive ink (ink 1) is ejected, and stripes by oblique lines are formed as shown in FIG. Formed (first printing step). At this time, the nozzles of the inkjet head are selected so that the nozzle spacing is evenly 280 μm, and the substrate temperature is adjusted to 70 ° C. with the heater at the lower part of the conveyance path from the selected nozzles on the substrate 1 × 10 ⁻¹⁰ The ink discharge amount was adjusted so as to be m ³ / m, and an ink line was formed. At this time, the droplet discharge frequency was 4.5 KHz. This line is dried immediately after formation, and further by controlling the drying conditions, the conductive material is selectively accumulated at the end by drying, and as a result, each ink line becomes two parallel lines with an interval of 140 μm. It was.

  Next, after stopping the substrate conveyance and returning a certain amount, the head array 61 is scanned from the opposite side to the left while the substrate is conveyed again in the substrate conveyance direction as shown in FIG. However, the conductive ink was ejected in the same manner as in the first printing process, and stripes with diagonal lines inclined in the opposite direction to the first printing process were formed (second printing process).

  Next, in the drying zone 8, air drying at 70 ° C. was performed for 5 minutes for drying to form a first layer. As a result, the first layer became a lattice pattern composed of diagonal lines.

  Next, in the low resistance zone 9, the first layer was heated in an oven at 120 ° C. for 1 hour.

  The relationship between the ink application area and the formation pattern of the first layer will be described with reference to FIGS.

  FIG. 16 is a diagram illustrating ink application regions in the first printing process and the second printing process. The hatched portion in the figure is the ink application area. As shown in the drawing, the line width of the conductive ink applied on the base material in each printing step is 140 μm after wetting and spreading on the base material, and these are arranged at a pitch of 280 μm.

  On the other hand, FIG. 17 shows a grid pattern formed of a first layer formed as a result of selectively depositing a conductive material on both ends of the line width direction. As shown in the figure, a conductive material is selectively deposited on both ends in the line width direction, so that two parallel lines (parallel lines) are generated from one line segment, and a lattice having a line interval of 140 μm is formed. Pattern is formed.

  In the present invention, the line segment of the conductive ink applied on the substrate has a line width after wetting and spreading (this line width is two parallel lines (parallel lines) generated from one line segment). Is preferably 100 to 400 μm. Moreover, it is preferable that the arrangement | positioning pitch of the line segment of the electroconductive ink provided on a base material is set to the range of 1.8 to 2.3 times the line width after wetting spreading. More preferably, it is set in the range of 1 times.

<Formation of second layer>
Subsequently, the area | region of the base material in which the 1st layer was formed was conveyed to the 2nd layer formation zone 10, and electrolytic copper plating was performed with the electrolytic plating apparatus.

In plating, power was supplied from the lead-out wiring and electrolytic plating was performed in the following plating bath. A copper plate for plating is connected to the anode, and a constant current of 0.30 A / dm ² with respect to the total area of the lead-out wiring portion and the first-layer thin wire portion, until the time when the thin-wire portion film thickness reaches the target film thickness Energized.
The line width was the value shown in Table 1. After completion of energization, it was thoroughly washed with water and dried.

<Plating bath 1>: Electrolytic copper plating 60 g of copper sulfate pentahydrate, 19 g of sulfuric acid, 2 g of 1N hydrochloric acid, and 5 g of a gloss-imparting agent (“ST901C” manufactured by Meltex Co., Ltd.) were prepared with a formulation for finishing to 1000 ml with ion-exchanged water.

  Sample No. For the first conductive pattern, the formation of the third layer was omitted.

<Evaluation method>
The following evaluation was performed about the obtained base material with an electroconductive pattern.

(1) Visibility Regarding the conductive pattern formed on the entire area of 20 cm in length and width, whether the line forming the grid of the conductive pattern can be identified while changing the distance between the conductive pattern and the eyes according to the following evaluation criteria. evaluated.

<Evaluation criteria>
5: Indistinguishable even at 5 cm.
4: If it is 10 cm, it cannot be identified.
3: If it is 15 cm, it cannot be identified.
2: If it is 20 cm, it cannot be identified.
1: Discernable even at 25 cm.

(2) Sheet resistance The sheet resistance of the electroconductive thin wire | line part which comprises an electroconductive pattern was measured by 4 terminal 4 probe method.
The average value measured by measuring 10 points was evaluated according to the following evaluation criteria.

<Evaluation criteria>
5: Less than 1.0Ω / □.
4: It is 1.0Ω / □ or more and less than 5.0Ω / □.
3: More than 5.0Ω / □ and less than 10.0Ω / □.
2: More than 10.0Ω / □ and less than 50Ω / □.
1: 50Ω / □ or more.
(3) Adhesiveness It evaluated based on the tape peeling method and the crosscut method. That is, 25 square cuts (cross cut) were made in the substrate with conductive pattern, and the number of squares where film peeling occurred due to tape peeling was measured. Three base materials with conductive patterns were prepared, and the measured values in three tests were averaged and evaluated according to the following evaluation criteria.

<Evaluation criteria>
5: The number of cells where film peeling occurred was 0 cell.
4: The number of cells in which film peeling occurred was 1-2 cells.
3: The number of cells where film peeling occurred was 3-5 cells.
2: The number of cells where film peeling occurred was 6-10 cells.
1: The number of cells where film peeling occurred was 11-25 cells.

(4) Bending resistance As shown in FIG. 18, the substrate with the conductive pattern is reciprocated and bent with the surface on which the conductive pattern is formed on a cylinder having a diameter of 10 mm and bent. The decreasing rate of the resistance value of the conductive pattern before and after was measured, and the measured value was evaluated according to the following evaluation criteria. When the test is applied to a substrate having a conductive pattern on both sides, the same reciprocation is performed over a cylinder with either side facing up, and the rate of decrease in resistance value for the conductive pattern on the surface Was measured.

<Evaluation criteria>
5: Less than 5% 4: Less than 10% 3: Less than 20% 2: Less than 21-50% 1: More than 50%

(5) Durability (Heat and humidity durability)
The substrate with a conductive pattern was stored for 500 hours in an environment of 85 ° C. and relative humidity of 85%, and after returning to a room temperature and normal pressure environment, the rate of decrease in resistance value was measured, and the measured values were evaluated according to the following evaluation criteria. .

<Evaluation criteria>
5: Less than 5% 4: Less than 10% 3: Less than 20% 2: Less than 21-50% 1: More than 50%

  The above evaluation results are shown in Table 1.

(Sample No. 2)
In Example 1, the ink 1 (silver nanoparticle-containing ink 1) forming the first layer is replaced with the ink 2 (silver nanoparticle-containing ink 2), and the current density under electrolytic plating conditions is 0.50 A / dm ^2. Instead of this, a substrate with a conductive pattern was obtained in the same manner as in Example 1 except that the film densities of the first layer and the second layer were set to the values shown in Table 1.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 3)
In Example 1, the ink 1 (silver nanoparticle-containing ink 1) forming the first layer is replaced with the ink 3 (copper nanoparticle-containing ink), and the low-resistance treatment in the low-resistance zone 9 is performed in a reducing atmosphere. A substrate with a conductive pattern was obtained in the same manner as in Example 1 except that the heat treatment was performed at 0 ° C. and the laminated structure shown in Table 1 was used.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 4)
In Example 1, the ink 1 (silver nanoparticle-containing ink 1) forming the first layer was replaced with the ink 4 (silver powder-containing ink), and this was applied to the substrate by flexographic printing to obtain the laminated structure shown in Table 1. Except having done, it carried out similarly to Example 1, and obtained the base material with an electroconductive pattern.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 5)
In Example 1, the base material with a conductive pattern was obtained like Example 1 except having formed the 2nd layer with the following method.

<Formation of second layer>
Electrolytic silver plating was performed on the base material on which the first layer was formed using the following plating bath 2.

In plating, power was supplied from the lead wiring and electrolytic silver plating was performed in the following plating bath. A silver plate for plating is connected to the anode, and the time at which the thickness of the thin line portion reaches the target film thickness is 0.30 A / dm ² with respect to the total area of the lead-out wiring portion and the thin line portion of the first layer. Energized until. The line width was the value shown in Table 1. After completion of energization, it was thoroughly washed with water and dried.

<Plating bath 2>; Electrolytic silver plating 35 g of silver cyanide, 80 g of potassium cyanide, and 10 g of potassium carbonate were prepared with a formulation for finishing to 1000 ml with ion-exchanged water.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 6)
A substrate with a conductive pattern was obtained in the same manner as in Example 1 except that the substrate 3 was replaced with the substrate 1 in Example 1.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 7)
A substrate with a conductive pattern was obtained in the same manner as in Example 1 except that the substrate 3 was replaced with the substrate 2 in Example 1.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 8)
A substrate with a conductive pattern was obtained in the same manner as in Example 1 except that the substrate 3 was replaced with the substrate 4 in Example 1.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 9)
In Example 1, the third layer was further formed on the opposite side of the second layer from the first layer by the following method, and the conductive structure was the same as in Example 1 except that the laminated structure shown in Table 1 was used. A patterned substrate was obtained.

<Formation of third layer>
Electrolytic nickel plating was performed on the base material on which the second layer was formed using the following plating bath 2.

In plating, power was supplied from the lead-out wiring, and electrolytic plating was performed in the plating bath 3 described below. A nickel plate for plating is connected to the anode, and the target film whose thickness is shown in Table 1 at a constant current of 0.05 A / dm ² with respect to the total area of the lead-out wiring portion and the thin wire portion of the first layer. It was energized until it became thick. The line width was the value shown in Table 1. After completion of energization, it was thoroughly washed with water and dried.

<Plating bath 3>; Electrolytic nickel plating 240 g of nickel sulfate, 45 g of nickel chloride, and 30 g of boric acid were prepared with a formulation for finishing to 1000 ml with ion-exchanged water.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 10)
In Example 1, the third layer was further formed on the opposite side of the second layer from the first layer by the following method, and the conductive structure was the same as in Example 1 except that the laminated structure shown in Table 1 was used. A patterned substrate was obtained.

<Formation of third layer>
Electroless nickel plating was performed on the base material on which the second layer was formed using the following plating bath 4.

  The electroless plating time was performed until the predetermined film thickness shown in Table 1 was reached. The line width was the value shown in Table 1.

<Plating bath 4>: Electroless nickel plating 26 g of nickel sulfate, 60 g of sodium citrate, 21 g of sodium hypophosphite, and ammonium sulfate were prepared with a formulation for finishing with 1000 ml of ion-exchanged water. The plating bath temperature was 90 ° C.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

(Sample No. 11)
In Example 1, the third layer was further formed on the opposite side of the second layer from the first layer by the following method, and the conductive structure was the same as in Example 1 except that the laminated structure shown in Table 1 was used. A patterned substrate was obtained.

<Formation of third layer>
The base material on which the second layer is formed is subjected to electrodeposition coating by a conventional method in a bath using a mixture of carbon black and a water-soluble electrodeposition resin, and has an organic film thickness and line width shown in Table 1. A third layer made of a film was formed.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1. However, sample No. In No. 7, since an organic film was used for the third layer, the sheet resistance was not measured, and the resistance between terminals between which the organic film was not provided was measured. As a result, separately measured sample No. 1 was confirmed to be substantially the same value as the inter-terminal resistance between the end portions.

(Sample No. 12) * Comparison In Example 1, the ink discharge amount was adjusted to be 4 × 10 ⁻¹⁰ m ³ / m on the base material adjusted to 40 ° C., and an ink line was formed. Except having set it as the laminated structure, it carried out similarly to Example 1, and obtained the base material with a conductive pattern.

  About the obtained base material with an electroconductive pattern, the result evaluated similarly to Example 1 is shown in Table 1.

<Evaluation>
From Table 1, the sample no. The conductive patterns 1 to 11 and the substrate (substrate with a conductive pattern) provided with the conductive pattern can reduce the visibility of the conductive thin wire, can reduce the resistance value, and can bond the substrate and the conductive pattern. It can be seen that the property (adhesiveness) can be improved, the resistance value can be prevented from fluctuating even when the substrate is bent, and durability such as heat and humidity resistance can be imparted.

  Sample No. 1 and sample no. Compared with Sample No. 2, the film density of the second layer is higher than the film density of the first layer. It can be seen that No. 1 is further excellent in adhesion and bending resistance.

  Sample No. using silver powder In No. 4, sample No. using silver nano-ink was used. Compared to 1, the effect of the present invention is slightly inferior, but since silver is used, for example, compared to the case of using palladium or the like that requires reduction treatment for resistance reduction, the burden of the resistance reduction treatment (treatment Time).

  Sample No. 1 and sample no. From the comparison of FIG. 1 shows that it is further excellent in adhesiveness and bending resistance.

  Sample Nos. With different substrates were used. From the comparison of 1, 6, 7 and 8, it can be seen that by making the surface energy of the substrate 50 mN / m or more, the visibility of the conductive thin wire can be further reduced and the adhesion and bending resistance can be further improved.

  Sample No. provided with the third layer. Nos. 9, 10 and 11 are sample Nos. With no third layer. It can be seen that compared to 1, it is further excellent in heat and humidity resistance.

  On the other hand, Sample No. with a conductive thin wire having a line width of 10 μm or more. No. 12 (comparison) shows that the visibility of the conductive thin wire cannot be sufficiently lowered, and the adhesiveness, bending resistance, and heat and humidity resistance are poor.

1: Substrate 2: Conductive thin wire 21: First layer 22: Second layer 23: Third layer 3: Current collector 4: Wiring

Claims (21)

It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. A conductive pattern comprising a second layer containing metal as a main component.   The conductive pattern according to claim 1, wherein the first layer and the second layer have different film densities.   The conductive pattern according to claim 1, wherein the surface of the conductive thin wire has an arithmetic average roughness Ra of 200 nm or more and less than 2000 nm.   The conductive pattern according to claim 1, wherein the first layer is mainly composed of silver or copper, and the second layer is mainly composed of copper.   The conductive pattern according to claim 1, further comprising a third layer on the opposite side of the second layer from the first layer. On the base material subjected to the surface treatment, a pattern made of conductive thin wires having a line width of less than 10 μm is provided,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. The base material with an electroconductive pattern which uses as a component the 2nd layer which has a metal as a main component.   The substrate with a conductive pattern according to claim 6, wherein the surface treatment is a treatment for increasing the surface energy of the substrate.   The substrate with a conductive pattern according to claim 6 or 7, wherein the surface treatment is a treatment for forming a resin layer on the surface of the substrate.   The base material with an electroconductive pattern in any one of Claims 6-8 in which the pattern which consists of the said electroconductive fine wire of less than the said line width of 10 micrometers is provided in both surfaces of the said base material which performed the surface treatment on both surfaces. A method for producing a substrate with a conductive pattern according to any one of claims 6 to 9,
The forming process of the first layer includes a printing process, and the printing process forms a line segment using an ink having a conductive material concentration of less than 5%, and then controls the drying process of the ink, and the line width of the line segment The manufacturing method of the base material with a conductive pattern including the process of selectively depositing a conductive material on the direction both ends.   The method for producing a substrate with a conductive pattern according to claim 10, wherein the surface tension of the ink is less than 50 mN / m, and the contact angle of the ink with respect to the substrate is in the range of 10 ° to 50 °.   The manufacturing method of the base material with an electroconductive pattern of Claim 10 or 11 which uses the inkjet method for formation of the said line segment in the said printing process.   The manufacturing method of the base material with an electroconductive pattern of Claim 12 which prints in multiple times from several directions with respect to the said base material using the inkjet method, and forms the said line segment.   The ink drying process is a combination of one or more selected from a process of drying the substrate during printing, a process of heating after printing, a process of blowing air after printing, and a process of irradiating light after printing. Item 14. A method for producing a substrate with a conductive pattern according to any one of Items 10 to 13.   The electrical conductivity according to any one of claims 10 to 14, wherein the resistance is reduced by a process selected from heat treatment, chemical treatment, and light (irradiation) treatment as a subsequent step of the process of selectively depositing the conductive material. A method for producing a patterned substrate.   The manufacturing method of the base material with an electroconductive pattern in any one of Claims 10-15 including an electrochemical process as a formation process of a said 2nd layer.   The method for producing a substrate with a conductive pattern according to claim 16, wherein the electrochemical process is one of electroless plating and electrolytic plating, or a combination of both.   The manufacturing method of the base material with a conductive pattern in any one of Claims 10-17 which forms a 3rd layer on the said 2nd layer.   The manufacturing method of the base material with a conductive pattern in any one of Claims 10-18 which forms a current collection line so that at least one part of the said conductive pattern may contact. A structure having a conductive pattern on the surface,
The conductive pattern is
It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. The structure which has the 2nd layer which has a metal as a main component, and a component. A structure manufacturing method for manufacturing the structure according to claim 20,
It is a pattern composed of conductive thin wires having a line width of less than 10 μm,
At least a part of the thin wire has a multilayer structure,
The multilayer structure includes a first layer having a thickness of less than 500 nm containing one or more conductive materials selected from conductive particles, conductive fillers, and conductive wires, and a thickness greater than that of the first layer. Using a base material with a conductive pattern provided on the surface treated with a conductive pattern comprising a second layer containing a metal as a main component and a component,
A structure for manufacturing a structure having a conductive pattern on its surface by bonding the substrate with a conductive pattern to the structure surface or transferring a conductive pattern portion from the substrate with a conductive pattern. Production method.

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