JP2018196992A - Functional fine line pattern, substrate with transparent conductive film, device, and electronic device - Google Patents

Abstract

To provide a functional fine line pattern, a transparent conductive film, a device, and an electronic device capable of forming functional fine lines stably with high freedom degree.SOLUTION: There are provided a functional fine line pattern, in which a plurality of polygonal fine lines 32 (52) containing a functional material are arranged in parallel on a substrate 1 two-dimensionally, and at least a pair of the polygonal fine lines 32 (52) are connected at 2 intersection points by crossing both sides sandwiching an apex of the polygonal each other; a substrate with a transparent conductive film having the transparent conductive film consisting of the functional fine line pattern on a substrate surface; a device having the substrate with the transparent conductive film; and an electronic device having the device.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a functional fine line pattern, a substrate with a transparent conductive film, a device, and an electronic apparatus that can stably form a functional fine line with a high degree of freedom.

  In Patent Documents 1 to 3, when a droplet containing a conductive material applied on a base material is dried, a conductive material is selectively applied to the peripheral portion of the droplet by utilizing a coffee stain phenomenon. Techniques for depositing are disclosed. In Patent Document 1, by applying droplets in the form of dots, ring-shaped conductive thin wires are formed on the periphery of the droplets. In Patent Documents 2 and 3, by applying droplets in a linear form, linear conductive thin wires are formed on the peripheral edge of the droplets.

WO2011 / 051952 JP 2005-95787 A JP 2014-38992 A

  In the technique of Patent Document 1, in order to increase the diameter of the ring-shaped conductive thin wire, it is necessary to increase the diameter of the droplet applied in a dot shape. Moreover, in the technique of Patent Document 2, in order to increase the arrangement interval of the linear conductive thin wires, it is necessary to increase the line width of the droplets applied in a linear shape. As a result, it is necessary to apply a large amount of liquid to form droplets, and the drying load increases. When the drying load increases, it becomes difficult to stably form fine wires, and the tact time becomes long. As described above, in the conventional technique, it has been difficult to stably form a thin line with a high degree of freedom.

  For example, when forming a transparent conductive film used for touch panel sensors, etc. with an aggregate of conductive thin wires, if the conductive thin wires can be stably formed with a high degree of freedom, the resistance of the transparent conductive film can be reduced and the visibility can be further reduced. It becomes possible to improve the property (difficulty in visually recognizing the conductive thin wire). In addition, if a functional thin wire having various functions, not limited to a conductive thin wire, can be stably formed with a high degree of freedom, the function can be suitably exhibited.

  Accordingly, an object of the present invention is to provide a functional fine line pattern, a substrate with a transparent conductive film, a device, and an electronic apparatus that can stably form a functional fine line with a high degree of freedom.

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

  The above problems are solved by the following inventions.

1.
On the base material, a plurality of polygonal fine wires containing functional materials are arranged two-dimensionally,
A functional thin line pattern, wherein at least one pair of polygonal thin lines are connected at two intersections by intersecting both sides sandwiching the vertex of the polygon.
2.
2. The functional thin line pattern as described in 1 above, wherein the overlapping area of the internal regions of the polygonal thin lines connected to each other is 1/10 or less of the area of the internal region of each polygonal thin line.
3.
3. The functional thin line pattern according to 1 or 2, wherein the polygonal thin line is a triangle, a quadrangle, a hexagon, or an octagon.
4).
A plurality of the thin polygonal wires that are quadrangles whose sides are inclined with respect to the longitudinal direction of the base material are arranged in parallel at a predetermined pitch in each of the longitudinal direction and the width direction of the base material. 4. The functional thin line pattern as described in 3 above.
5.
5. The functional thin line pattern according to any one of 1 to 4, wherein the functional material is a conductive material.
6).
The functional fine wire pattern according to any one of 1 to 5, wherein the polygonal fine wire is covered with a plating layer.
7).
The functional thin line pattern according to any one of 1 to 6, wherein the functional thin line pattern is provided on both surfaces of the base material.
8).
A substrate with a transparent conductive film, comprising a transparent conductive film comprising the functional fine wire pattern according to any one of 1 to 7 above, wherein the functional material is a conductive material.
9.
9. A device comprising the substrate with a transparent conductive film as described in 8 above.
10.
An electronic apparatus comprising the device according to 9 above.

  ADVANTAGE OF THE INVENTION According to this invention, the functional fine wire pattern which can form a functional fine wire with high freedom stably, a base material with a transparent conductive film, a device, and an electronic device can be provided.

The perspective view explaining a mode that a fine line pattern is formed It is a figure explaining the flow which carries a functional material to the edge part of a liquid, Comprising: (a) is a figure which shows the case of the line-shaped liquid which consists of a closed geometric figure, (b) is a reference example, Diagram showing the case of a liquid that is not a closed geometric figure The figure explaining functional thin line pattern formation when a geometric figure is a rectangle The figure explaining functional thin line pattern formation when a geometric figure is a rectangle The figure explaining an example of an electrolytic plating process Diagram explaining the electroplated functional fine wire pattern The figure explaining the functional fine line pattern from which some fine lines were removed Fig. 7 The figure explaining an example in the case of forming a functional fine wire pattern on both surfaces of a base material The figure explaining an example of a touch panel sensor provided with the transparent conductive film comprised by the functional fine wire pattern The figure explaining functional thin line pattern formation when a geometric figure is a triangle Diagram explaining functional thin line pattern formation when geometric figure is hexagon Diagram explaining functional thin line pattern formation when geometric figure is octagon The figure explaining functional fine line pattern formation when a geometric figure is circular The figure explaining the other example of the connection form of the mutually adjacent thin wire | line unit Diagram explaining yet another example of geometric figure The perspective view which shows an example of the thin wire | line unit formed on the base material Optical micrograph of fine line pattern (1) of Example 1 consisting of inner fine line and outer fine line Optical micrograph of fine line pattern (2) of Example 2 with outer fine line plated Optical micrograph of fine line pattern (3) of Example 3 with inner fine lines removed

  By forming a closed geometric figure on the substrate with the line liquid containing the functional material, and then drying the line liquid to deposit the functional material along the edges. Then, a functional thin line unit (hereinafter also simply referred to as a thin line unit) composed of an inner thin line and an outer thin line containing a functional material is formed. A functional fine line pattern can be formed by arranging one or more fine line units on the substrate. Thereby, the effect that a functional fine wire can be formed stably with high flexibility is obtained.

  Furthermore, in a preferred embodiment, the fine line unit is used as a functional fine line pattern precursor (hereinafter also simply referred to as a precursor) for forming a functional fine line pattern. That is, by removing a part of the functional thin line composed of the inner thin line and the outer thin line constituting the precursor, a functional fine line pattern can be formed by the fine lines remaining without being removed. Thereby, the freedom degree of pattern formation can further be raised and the effect which can adjust the arrangement | positioning space | interval of the thin wire | line which comprises a functional thin wire | line pattern with a high freedom degree especially is acquired.

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

  First, a process of forming a thin line unit from a line liquid will be described with reference to FIG.

  As shown in FIG. 1A, a closed geometric figure is formed on a base material 1 by a line-like liquid 2. The geometric figure formed of the line-shaped liquid 2 includes an inner edge 21 and an outer edge 22 which are independent from each other as an edge by including a region 20 to which no liquid is applied. The inner edge 21 is an inner edge of the closed geometric figure formed by the line-shaped liquid 2 and is an edge adjacent to the region 20 to which no liquid is applied. The outer edge 22 is an outer edge of a closed geometric figure formed by the line-shaped liquid 2 and is not connected to the inner edge 21. When the liquid 2 is dried, a functional material is selectively deposited along the inner edge 21 and the outer edge 22 which are edges by using the coffee stain phenomenon, and the liquid 2 is shown in FIG. Thus, the inner thin line 31 is formed at a position corresponding to the inner edge 21, and the outer thin line 32 is formed at a position corresponding to the outer edge 22.

  In this way, the thin line unit 3 is formed which includes the inner thin line 31 containing the functional material and the outer thin line 32 surrounding the inner thin line 31. The inner thin wire 31 and the outer thin wire 32 constituting the thin wire unit 3 are not connected to each other and are independent. The inner thin line 31 and the outer thin line 32 are sufficiently thinner than the line width (line thickness) of the line-shaped liquid 2. In the illustrated example, the line-shaped liquid 2 has one inner edge 21 and one outer edge 22, thereby forming a thin line unit 3 including a pair of inner thin lines 31 and outer thin lines 32.

  The effect of forming the thin line unit 3 from the line liquid 2 will be described with reference to FIG.

  As shown in FIG. 2 (a), the drying of the line-shaped liquid 2 applied on the substrate 1 is faster at the inner edge 21 and the outer edge 22 than at the center, and therefore, first, the inner edge 21 and the outer edge 22 are dried. Along with the local deposition of functional material. The liquid edge is fixed by the deposited functional material (fixation of the contact line), and the shrinkage in the thickness direction of the line-shaped liquid 2 accompanying the subsequent drying is suppressed. In the line-shaped liquid 2, a flow from the central portion toward the inner edge 21 and a flow from the central portion toward the outer edge 22 so as to compensate for the liquid lost by evaporation at the inner edge 21 and the outer edge 22. It is formed. In the figure, the direction of flow is conceptually indicated by arrows. This flow causes additional functional material to be carried and deposited on the inner edge 21 and the outer edge 22. As a result, an inner fine line 31 and an outer fine line 32 containing a functional material are formed at positions corresponding to the inner edge 21 and the outer edge 22, respectively.

  As shown in the reference example of FIG. 2B, the functional material is selectively deposited on the edge 101 of the liquid 100 that is not a closed geometric figure, as shown in FIG. The line-shaped liquid 2 includes the region 20 to which no liquid is applied, so that the amount of liquid applied can be reduced and the drying load can be reduced. Thereby, tact time can be shortened and production efficiency can be improved.

  Furthermore, the line-like liquid 2 includes the region 20 to which no liquid is applied, so that the total amount of heat of vaporization accompanying the drying of the liquid becomes relatively small. Therefore, changes in the substrate temperature and non-uniformity due to drying are suppressed, and the above-described liquid flow can be stably formed.

  Furthermore, the line-shaped liquid 2 can shorten the average moving distance until the functional material reaches the edge by flow by including the region 20 to which no liquid is applied.

  As a result, even when the line-shaped liquid 2 is formed with a relatively large diameter, the coffee stain phenomenon can be stably expressed, and the formation of the inner fine line 31 and the outer fine line 32 can be stabilized. Thereby, the effect which can form stably the inner side fine wire 31 and the outer side fine wire 32 which are functional thin wires with a high degree of freedom is acquired.

  It is preferable to promote the formation of a flow that carries the functional material to the edge. For example, by adjusting conditions such as solids concentration, contact angle between liquid and substrate, amount of liquid, substrate heating temperature, liquid arrangement density, or environmental factors such as temperature, humidity, and pressure, the edge of the liquid Can be fixed at an early stage, and the difference in evaporation amount between the liquid central portion and the edge can be increased. Thereby, formation of the flow which carries a functional material to an edge can be accelerated | stimulated.

  Application of the line-shaped liquid 2 onto the substrate 1 can be performed by an ink jet method. Specifically, while moving an inkjet head included in a droplet ejection device (not shown) relative to the substrate, ink containing a functional material is ejected from the nozzles of the inkjet head, and the ejected ink droplets are placed on the substrate. Can be combined to form the line-shaped liquid 2. 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.

  By using the inkjet method, a closed geometric figure can be freely formed in a desired shape by the line liquid 2. Corresponding to the shape of the inner edge 21 and the outer edge 22 of the line-shaped liquid 2, the shapes of the inner fine line 31 and the outer fine line 32 constituting the obtained fine line unit 3 are respectively formed into desired closed geometric figures. Can be formed. Therefore, the functional fine line can be formed with a higher degree of freedom by using the inkjet method.

  Hereinafter, a specific example of a method of forming a transparent conductive film composed of a functional fine line pattern by forming a plurality of fine line units 3 on the substrate 1 and using the plurality of fine line units 3 as a precursor, The present invention will be described in more detail. Here, a conductive material is preferably used as the functional material, and a transparent substrate is preferably used as the base material.

  First, with reference to FIGS. 3 to 8, a mode in which a closed geometric figure made of a line-like liquid is made into a quadrangle will be described.

  First, as shown in FIG. 3A, a quadrangular shape is formed on the substrate 1 as a closed geometric figure by the first line-shaped liquid 2 containing a conductive material. Here, a plurality of quadrangular first line-shaped liquids 2 are arranged on the base material 1 at a predetermined pitch in the longitudinal direction (the vertical direction in the figure) and the width direction (the horizontal direction in the figure) of the base material. Yes. Here, for convenience, four first line-shaped liquids 2 are illustrated.

  The first line-like liquid 2 applied on the substrate 1 includes an inner edge 21 and an outer edge 22 that are independent from each other as an edge by including a region 20 to which no liquid is applied.

  Next, when the first line-shaped liquid 2 is dried, a coffee stain phenomenon occurs, and the conductive material is selectively deposited along the inner edge 21 and the outer edge 22 of the line-shaped liquid 2.

  Thereby, as shown in FIG.3 (b), the 1st thin wire | line unit 3 which consists of the inner fine wire 31 and the outer fine wire 32 is formed. The thin wires 31 and 32 constituting the first thin wire unit 3 are formed in a quadrangular shape.

  Next, as shown in FIG. 4A, a quadrangular shape is formed on the substrate 1 as a closed geometric figure by the second line-shaped liquid 4 containing a conductive material. Here, a plurality of quadrangular second line-shaped liquids 4 are arranged on the substrate 1 at a predetermined pitch in the longitudinal direction and the width direction of the substrate. Here, for convenience, five second linear liquids 4 are illustrated.

  The second line-like liquid 4 applied on the substrate 1 includes an inner edge 41 and an outer edge 42 that are independent from each other by including a region 40 to which no liquid is applied.

  In this embodiment, the second line-shaped liquid 4 is formed at a position sandwiched between the four first thin line units 3. The vicinity of each vertex of the quadrangle made of the second line-shaped liquid 4 is arranged so as to contact the outer fine line 32 of the adjacent first fine line unit 3. Each square vertex of the second line-shaped liquid 4 is arranged in a region between the inner thin line 31 and the outer thin line 32 of the adjacent first thin line unit 3.

  Next, when the second line-shaped liquid 4 is dried, a coffee stain phenomenon occurs, and the conductive material is selectively deposited along the inner edge 41 and the outer edge 42 of the second line-shaped liquid 4.

  Thereby, as shown in FIG.4 (b), the 2nd thin wire | line unit 5 which consists of the inner side fine wire 51 and the outer side fine wire 52 can be formed. The thin wires 51 and 52 constituting the second thin wire unit 5 are formed in a quadrangular shape.

  In this embodiment, the first fine wire unit 3 and the second fine wire unit 5 are alternately formed on the base material 1 in the longitudinal direction and the width direction of the base material. The outer fine wire 32 of the first fine wire unit 3 and the outer fine wire 52 of the second fine wire unit 5 are connected to each other, and the inner fine wire 31 of the first fine wire unit 3 and the inner fine wire 51 of the second fine wire unit 5 are not connected to each other. Thus, each thin wire | line unit 3 and 5 is formed. The inner thin wires 31 and 51 are not connected to the other inner thin wires 31 and 51 but are also not connected to the other outer thin wires 32 and 52.

  As described above, a pattern composed of the fine line units 3 and 5 connected to each other by the outer fine lines 32 and 52 is formed on the substrate 1.

  Next, electrolytic plating is performed on the obtained pattern. An example of the electrolytic plating process will be described with reference to FIG.

  As shown in FIG. 5, the power supply member 6 is brought into contact with a pattern composed of thin wire units 3 and 5 in a plating bath (not shown) to perform electrolytic plating. At this time, since the outer thin wires 32 and 52 are connected to each other, an energization path including the plurality of outer thin wires 32 and 52 is formed in a mesh shape. By energizing the power supply member 6 through the energization path, the outer thin wires 32 and 52 in the energization path are subjected to electrolytic plating.

  On the other hand, the inner thin wires 31, 51 are not connected to the other inner thin wires 31, 51 and the outer thin wires 32, 52, and are formed independently of each other. Is not formed. As shown in the figure, when the inner thin wires 31 and 51 that are in direct contact with the power supply member 6 are present, the inner thin wires 31 and 51 can be electroplated, but the other inner thin wires 31 and 51 are not energized. Electrolytic plating is not applied. When the power supply member 6 is not brought into contact with the inner thin wires 31, 51, neither of the inner thin wires 31, 51 is subjected to electrolytic plating.

  In this way, the outer fine wires 32 and 52 are energized through the energization path, whereby the outer thin wires 32 and 52 can be selectively subjected to electrolytic plating. Here, “selective” means that at least the number of outer thin wires 32 and 52 to which electrolytic plating is applied is larger than the number of inner thin wires 31 and 51 to which electrolytic plating is applied.

  In this way, as shown in FIG. 6, the film thickness of the outer fine wires 32 and 52 that have been subjected to electrolytic plating can be increased compared to the inner thin wires 31 and 51 that have not been subjected to electrolytic plating. As a result, the outer thin wires 32 and 52 have a lower resistance than the inner thin wires 31 and 51, and the durability is further improved.

  Next, a functional thin line pattern is formed using the thin line units 3 and 5 as precursors.

  In this embodiment, by removing the inner thin lines 31 and 51 of the thin line units 3 and 5, as shown in FIG. 7, a functional fine line pattern is formed by the outer thin lines 32 and 52 connected to each other to remain without being removed. doing.

  As described above, by applying electrolytic plating to the outer thin wires 32 and 52 to increase the film thickness, the outer thin wires 32 and 52 are not easily removed, and the inner thin wires 31 and 51 not subjected to electrolytic plating are compared. The effect which can be removed easily is obtained.

  The method for removing the fine line is not particularly limited, but it is preferable to use, for example, a method of irradiating energy rays such as laser light or a method of chemically etching.

  As a preferred method for removing the fine wires, a method of removing the inner fine wires 31 and 51 with a plating solution when electrolytic plating is performed on the outer fine wires 32 and 52 can be used. In this case, a plating solution that can dissolve or decompose the conductive material constituting the fine wire to be removed can be used.

  As a specific example, first, fine wire units 3 and 5 including inner fine wires 31 and 51 and outer fine wires 32 and 52 are formed using silver nanoparticles as a conductive material. Then, a copper plating layer is selectively provided on the outer thin wires 32 and 52 as the first electrolytic plating, and then a nickel plating layer is provided on the copper plating layer as the second electrolytic plating. At this time, the inner fine wires 31 and 51 made of silver not subjected to the first electrolytic plating can be dissolved or decomposed and removed by the plating solution of the second electrolytic plating (electrolytic nickel plating). As described above, it is preferable that the electrolytic plating on the outer fine wires 32 and 52 and the removal of the inner fine wires 31 and 51 proceed simultaneously.

  In addition, for example, after the power supply for electrolytic plating is stopped, the substrate 1 is allowed to have a sufficient time to remove the thin wires to be removed, preferably the inner thin wires 31 and 51, preferably for 1 to 30 minutes. It is also preferable to immerse in a plating solution.

  As described above, by removing the inner thin lines 31 and 51, the arrangement interval of the thin lines in the functional thin line pattern including the outer thin lines 32 and 52 that remain without being removed can be adjusted with a high degree of freedom. The adjustment of the arrangement interval by partially removing the thin line is particularly advantageous when the arrangement interval is increased.

  By removing a part of the fine lines and increasing the arrangement interval of the fine lines, an effect of suitably improving the transmittance and low visibility of the transparent conductive film made of the functional fine line pattern can be obtained.

  The functional thin line pattern obtained as described above will be described in detail.

  The functional fine line pattern shown in FIG. 7 is formed by two-dimensionally arranging a plurality of fine lines composed of outer fine lines 32 and 52 on the base material 1, that is, rectangular fine lines containing a functional material. A plurality of rectangular fine wires (outer fine wires 32 and 52) are arranged in parallel at a predetermined pitch in each of the longitudinal direction and the width direction of the substrate 1.

  As shown in FIG. 7, in the functional fine line pattern, the quadrangular fine lines (outer fine lines 32 and 52) are quadrangles whose sides are inclined (45 ° in the illustrated example) with respect to the longitudinal direction of the substrate 1. It is preferable. Thereby, the effect which can prevent suitably the moire generation | occurrence | production at the time of incorporating the base material 1 with a transparent conductive film which consists of a functional fine wire pattern in devices, such as an image display apparatus, is acquired.

  Moire means that when a substrate 1 with a transparent conductive film made of an aggregate of conductive thin wires is incorporated into a device, streaks derived from combinations of the conductive thin wires and other elements in the device are visually recognized. That is. Moire can be caused by, for example, optical interference between a conductive thin wire constituting a transparent conductive film and a pixel array included in an image display element in the device. By preventing moiré, an effect of clearly viewing an image displayed by the image display element can be obtained.

  In such a functional fine line pattern, adjacent quadrilateral fine lines (outer fine lines 32 and 52) are connected at two intersections by intersecting both sides sandwiching the apex of the quadrangle. That is, as shown in an enlarged view in FIG. 8, adjacent rectangular fine lines (outer fine lines 32 and 52) have both sides a 1 and a 2 sandwiching the vertex A of one rectangular fine line (outer fine line 32) and the other square. By connecting both sides b1 and b2 sandwiching the apex B of the shape fine line (outer fine line 52), the two intersections C and D are connected. In FIG. 8, for convenience of explanation, only a pair of adjacent rectangular thin lines (outer thin lines 32 and 52) are shown. However, as shown in FIG. It is connected. By connecting the adjacent rectangular fine wires (outer fine wires 32 and 52) at the intersection of two points in this way, the two rectangular fine wires can be reliably connected, particularly when a conductive material is used as the functional material. Electrical connection can be realized. As a result, the resistance of the transparent conductive film can be further reduced, and the effect of suitably preventing non-uniform resistance can be obtained.

  Moreover, it is preferable that the overlapping area of the inner regions of adjacent rectangular fine wires (outer thin wires 32, 52) is 1/10 or less of the area of the inner region of each rectangular fine wire (outer thin wires 32, 52). Here, the overlapping area is an area of a quadrangle ADBC having four vertices including two vertices A and B and two intersections C and D as vertices in the illustrated example. Thereby, while being able to connect both square-shaped fine wires more reliably, the effect that a functional fine wire pattern becomes difficult to visually recognize is acquired.

  In particular, when a conductive material is used as the functional material, more reliable electrical connection can be realized by covering the rectangular fine wires (outer fine wires 32 and 52) with a plating layer.

  In the above description, the case where the functional thin line pattern is formed on one surface of the base material has been described. However, it is also preferable that the functional thin line pattern is formed on both surfaces of the base material. An example in the case of forming a functional thin line pattern on both surfaces of a base material is demonstrated with reference to FIG.

  In the example of FIG. 9, a functional thin line pattern is formed on one surface (front surface) of the substrate 1, and further, a functional thin line pattern is formed on the other surface (back surface) of the substrate 1.

  Here, the functional thin line pattern on each surface is the same as that shown in FIG. 7, and the outer thin lines 32, 52 that remain without being removed by removing the inner thin lines 31, 51 of the thin line units 3, 5 are removed. It is comprised by.

  Thus, when forming a functional fine line pattern on both surfaces of the base material 1, it is particularly preferable to increase the arrangement interval of the fine lines by removing a part of the fine lines constituting the fine line unit on one side and / or the other side. .

For example, by using a transparent base material as a base material and using a conductive material as a functional material to be included in the functional thin wire patterns on both sides, a transparent conductive film composed of the functional thin wire patterns is formed on both surfaces of the transparent base material. be able to. In this case, the requirement for high alignment accuracy of the front and back patterns can be relaxed by increasing the arrangement interval of the fine lines by partially removing the fine lines.
In other words, even if there is a slight shift in the alignment of the front and back patterns, the appearance of bone due to interference between the front and back patterns can be suitably prevented due to the large thin line spacing. A transparent substrate provided with a transparent conductive film on both sides can be suitably used as, for example, a touch panel sensor.

  FIG. 10 shows an example of a touch panel sensor including a transparent conductive film configured by a functional thin line pattern. FIG. 10A shows a state in which the base material 1 is viewed from the front surface side, and FIG. 10B shows a state in which the base material 1 is viewed from the back surface side.

  In the illustrated touch panel sensor, as shown in FIG. 10A, a plurality of strip-shaped X electrodes 7 are arranged in parallel on the surface of a transparent substrate 1. The plurality of X electrodes 7 are each constituted by a transparent conductive film 8 formed by a functional thin line pattern composed of outer thin lines 32 and 52.

  In the functional fine line pattern constituting each transparent conductive film 8, the adjacent outer fine lines 32 and 52 are connected to each other. On the other hand, the outer fine wires 32 and 52 constituting one transparent conductive film 8 are not connected to the outer fine wires 32 and 52 constituting the other transparent conductive film 8. Thus, the presence of the outer thin wires 32 and 52 that are not connected to each other makes it possible to form a plurality of independent X electrodes 7 that are not electrically connected to each other on the surface of the substrate 1. Each X electrode 7 is constituted by an aggregate composed of a plurality of outer fine wires 32 and 52 that are electrically connected to each other. In the figure, reference numeral 9 denotes a lead wiring, and each X electrode 7 is connected to a control circuit (not shown) by the lead wiring 9.

  On the other hand, as shown in FIG. 10B, a plurality of strip-shaped Y electrodes 10 are arranged in parallel on the back surface of the transparent substrate 1. Each of the plurality of Y electrodes 10 is formed of a transparent conductive film 8 formed of a functional thin line pattern including outer thin lines 32 and 52, similarly to the X electrode 7 described above. The strip-shaped Y electrode 10 is formed so that its longitudinal direction intersects the longitudinal direction of the X electrode described above. Each Y electrode 10 is connected to a control circuit (not shown) by a lead wiring 9.

  The X electrode 7 and the Y electrode 10 are provided so as to intersect (overlap) via the transparent substrate 1. At this time, the partial spacing of the fine lines in the functional fine line pattern constituting the transparent conductive film constituting the X electrode 7 and the Y electrode 10 is increased by partially removing the fine lines described above. As described above, it is possible to relax the requirement for high alignment accuracy of the front and back patterns.

  The touch panel sensor having the above-described configuration can be suitably used as, for example, a capacitive touch panel sensor. If it is a capacitive touch panel, using the induced current based on the capacitance change that occurs when the user's finger or conductor approaches or contacts these X electrode 7 and Y electrode 10 during operation, The position coordinates of a finger, a conductor, etc. can be detected.

  In the above description, the process from the formation of the first line-shaped liquid to the formation of the first thin line unit and the process from the formation of the second line-shaped liquid to the formation of the second thin line unit are provided twice. A plurality of thin line units are formed separately, but the present invention is not limited to this. After forming the second thin line unit, one or more additional thin line units may be formed. Further one or more thin wire units can be formed in one or more times. That is, when a plurality of thin line units are formed on the substrate, they can be appropriately divided into a plurality of times. In addition, for example, when the thin line units are not connected to each other, it is also preferable to form a plurality of thin line units at a time.

  In the above description, a case has been described in which a closed geometric figure made of a line-like liquid is a quadrilateral and a functional fine line pattern made of a square-like fine line is formed. However, the present invention is not limited to this. The closed geometric figure made of can be made a polygon, and a functional fine line pattern made of polygonal fine lines can be formed.

  Below, the case of a triangle, a hexagon, and an octagon is demonstrated as an example of polygons other than a rectangle.

  By forming a closed geometric figure made of a line-shaped liquid into a triangle, as shown in FIG. 11A, a fine line unit 3 made up of an inner fine line 31 and an outer fine line 32 each formed in a triangular shape is formed. be able to. The adjacent outer fine lines 32 are connected at two intersections by intersecting both sides sandwiching the apex of the triangle.

  By removing the inner fine line 31 of the functional fine line pattern precursor composed of the fine line unit 3, as shown in FIG. 11B, the outer fine line 32 that remains without being removed, that is, the functional fine line composed of a triangular thin line. A pattern can be formed.

  By forming a closed geometric figure made of a line-shaped liquid into a hexagon, as shown in FIG. 12A, a fine line unit 3 made up of an inner fine line 31 and an outer fine line 32 each formed in a hexagonal shape is formed. can do. The adjacent outer fine lines 32 are connected at two intersections by intersecting both sides sandwiching the hexagonal apex.

  By removing the inner fine line 31 of the functional fine line pattern precursor composed of the fine line unit 3, as shown in FIG. 12B, the outer fine line 32 that remains without being removed, that is, the hexagonal fine line is two-dimensionally. A plurality of functional fine line patterns formed in parallel can be formed.

  By forming a closed geometric figure made of a line-shaped liquid into an octagon, as shown in FIG. 13 (a), a thin line unit 3 consisting of an inner thin line 31 and an outer thin line 32 each formed in an octagon is formed. can do. Adjacent outer thin wires 32 are connected at two intersections by intersecting both sides sandwiching the octagonal apex.

  By removing the inner fine line 31 of the functional fine line pattern precursor composed of the fine line unit 3, as shown in FIG. 13B, the outer fine line 32 that remains without being removed, that is, the octagonal fine line is two-dimensionally. A plurality of functional fine line patterns formed in parallel can be formed.

  Furthermore, the closed geometric figure made of the line-shaped liquid is not limited to a polygon, and may include a curved element such as a circle or an ellipse. FIG. 14 shows an example in which a closed geometric figure made of a line-like liquid is circular.

  By forming the closed geometric figure made of the line-like liquid into a circle, as shown in FIG. 14A, the fine line unit 3 composed of the inner fine line 31 and the outer fine line 32 each formed in a circular shape is formed. be able to. Adjacent outer fine lines 32 are connected at two intersections by intersecting circular circumferences.

  By removing the inner fine line 61 of the functional fine line pattern precursor composed of the fine line unit 3, as shown in FIG. 14B, the outer fine line 62 that remains without being removed, that is, the circular fine line is two-dimensionally. A plurality of functional fine line patterns formed in parallel can be formed.

  When the functional thin line pattern is configured by polygonal thin lines (outer thin lines 32), the length of one side of the polygon can be freely adjusted. For example, the length of one side is preferably 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, and more preferably 1 mm or more. Even when such a relatively large polygon is formed, a stable thin line can be formed by applying the line-like liquid as a closed geometric figure. Since stable thin line formation can be realized regardless of the size, the upper limit of the length of one side is not particularly limited, and can be appropriately set according to the application. It is preferable that at least one side constituting the polygon is in the above range, and it is more preferable that all sides are in the above range.

  Further, the polygon is not limited to a regular polygon, and the length of each side constituting the polygon and the angle of each inner angle may be different from each other.

  In addition, even when the functional thin line pattern is formed by circular thin lines (outer thin lines 32), the circular diameter can be freely adjusted. For example, the diameter is preferably 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, and more preferably 1 mm or more. Even when such a relatively large circle is formed, a stable fine line can be formed by applying the line-like liquid as a closed geometric figure. Since stable thin wire formation can be realized regardless of the size, the upper limit of the diameter is not particularly limited, and can be appropriately set according to the application.

  In addition, when the functional fine line pattern is constituted by elliptic thin lines (outer fine lines 32), the above-described preferable range of the diameter can be applied as the preferable range of the long diameter.

  In the above description, when a plurality of fine line units are formed on the base material, the case where the plurality of fine line units are formed at a predetermined pitch has been mainly described, but the present invention is not limited to this.

  In the above description, when connecting the thin line units, the case where the outer thin lines are connected to each other and the inner thin line is not connected to the other inner thin lines and the outer thin line is mainly shown, but the present invention is not limited to this. Any of the functional thin wires constituting the thin wire unit can be brought into contact with each other and connected. For example, the inner thin wire and / or the outer thin wire of the first thin wire unit can be connected to the inner thin wire and / or the outer thin wire of the second thin wire unit. Below, with reference to FIG. 15, the other example of the connection form of a thin wire | line unit is demonstrated.

  In the example of FIG. 15A, the adjacent thin wire units 3, 5 are connected to the outer thin wires 32, 52, and are not connected to the inner thin wires 31, 51. In this example, the inner thin wire 31 constituting one thin wire unit 3 is connected to the outer thin wire 52 constituting the other thin wire unit 5. Similarly, the inner thin wire 51 constituting the other thin wire unit 5 is connected to the outer fine wire 32 constituting the one thin wire unit 3.

  In the example of FIG. 15B, the adjacent fine line units 3 and 5 are connected to the outer fine lines 32 and 52, and are also connected to the inner fine lines 31 and 51. In this example, the inner thin wire 31 constituting one thin wire unit 3 is connected to the outer thin wire 52 constituting the other thin wire unit 5. Similarly, the inner thin wire 51 constituting the other thin wire unit 5 is connected to the outer fine wire 32 constituting the one thin wire unit 3.

  By using the connection form shown in FIGS. 15A and 15B, for example, the above-described electrolytic plating can be suitably applied not only to the outer fine wire but also to the inner fine wire.

  When a plurality of thin line units connected to each other are formed, they may be connected by the same connection form, or various connection forms may be mixed. Further, some of the thin wire units may be arranged side by side in a state where neither the inner fine wire nor the outer fine wire is connected.

  In the above description, the case where the functional thin lines constituting the functional thin line pattern are connected by intersecting at two points is mainly shown, but the present invention is not limited to the connection at two points. For example, the functional thin wires may be connected at a single point. It is also preferable from the viewpoint of ensuring conductivity to connect two points of intersection and one point of contact as appropriate to connect at three or more points.

  Still another example of a closed geometric figure made of a line-like liquid will be described with reference to FIG.

  For example, as shown in FIG. 16A, it is also preferable that the closed geometric figure formed by the line-like liquid 2 is composed of zigzag elements. By drying this, the inner thin line and the outer thin line formed by the zigzag elements can be formed at positions corresponding to the zigzag inner edge 21 and the outer edge 22. Further, although not shown, a wavy element may be used instead of the zigzag element, or a zigzag element and a wavy element may be combined. When connecting functional thin lines that are not regular polygons, such as functional thin lines composed of zigzag elements and wavy line elements, they may be connected at one point or two points. The above connection can be preferably used. Preferred examples of the functional thin line that is not a regular polygon include a polygonal functional thin line having one or more interior angles larger than 180 °.

  As shown in FIG. 16B, the closed geometric figure formed by the line-shaped liquid 2 can include two regions 20a and 20b to which no liquid is applied. Thereby, the geometric figure can have a plurality of inner edges 21a, 21b. By drying this, one outer fine line can be formed at a position corresponding to the outer edge 22, and two inner thin lines can be formed at positions corresponding to the two inner edges 21a and 21b. It is also possible to set the number of areas to which the liquid contained in the line-shaped liquid 2 is not applied to be 3 or more, and thereby it is possible to form the number of inner fine lines corresponding to the number of the areas.

  Furthermore, as shown in FIG. 16 (c), the closed geometric figure formed by the line-shaped liquid 2 may include a protrusion 23. The protrusion 23 can be, for example, a line segment connected at one end to a closed geometric figure as shown in the figure.

  Further, the shape of the inner edge and the shape of the outer edge may be the same (that is, similar) or may be different. By making these shapes different, the shape of the inner fine wire and the shape of the outer fine wire in the obtained fine wire unit can be made different.

  A plurality of different geometric figures may be formed by a plurality of line-shaped liquids provided on the substrate. Thereby, the functional fine line pattern which combined the functional thin line which consists of multiple types of mutually different geometric figures can be formed. For example, the first line-shaped liquid and the second line-shaped liquid described above are preferably the same shape, but are not limited to this, and may be similar or different, for example, a combination of a square and a circle. It may be a shape.

  In the above description, the case where the functional fine line pattern is formed by removing the inner fine lines constituting the fine line unit by the outer fine lines remaining without being removed is not limited to this. A functional fine line pattern can be formed by fine lines that remain without being removed by removing any part of the fine lines composed of the inner fine line and the outer fine line constituting the fine line unit. For example, it is also preferable to form a functional fine line pattern by removing the outer fine lines constituting the fine line unit and leaving the inner fine lines remaining without being removed.

  In particular, as described with reference to FIGS. 1 and 2, the inner and outer thin lines constituting the thin line unit can be formed stably with a high degree of freedom. Not limited to this, it is also preferable to use one or a plurality of the fine line units arranged on the base material as the functional fine line pattern.

  In the above description, the case where the electroplating is selectively applied to the outer fine wires constituting the fine wire unit has been mainly described, but the present invention is not limited to this. For example, it is also preferable to apply electrolytic plating to both the inner and outer fine wires.

  In addition, it is also preferable to perform electrolytic plating on the outer fine wire after removing the inner fine wire constituting the fine wire unit, or to apply electrolytic plating to the inner fine wire after removing the outer fine wire constituting the fine wire unit. It is.

  The plating metal used for electrolytic plating is not particularly limited, but it is preferable to use, for example, copper or nickel. It is also preferable to laminate a plurality of plating layers on the fine wire. In this case, electrolytic plating is performed a plurality of times with different plating metals. For example, a method of improving the weather resistance by providing a copper plating layer on the fine wire as the first electrolytic plating to improve conductivity, and then providing a nickel plating layer on the copper plating layer as the second electrolytic plating is preferably exemplified. be able to.

  Moreover, it is also preferable to use electroless plating as well as electrolytic plating. Thereby, even when the functional material is not a conductive material, a plating layer can be provided on the fine line.

  The functional material contained in the liquid (ink) for forming the line-shaped liquid is not particularly limited as long as it is a material for imparting a specific function to the substrate. Giving a specific function means, for example, imparting conductivity to a substrate using a conductive material, or imparting insulation to a substrate using an insulating material. The functional material is preferably a material different from the material constituting the substrate surface to which the functional material is applied. Preferred examples of the functional material include a conductive material, an insulating material, a semiconductor material, an optical filter material, and a dielectric material. In particular, the functional material is preferably a conductive material or a conductive material precursor. An electroconductive material precursor refers to what can be changed into an electroconductive material by performing an appropriate process.

  Preferred examples of the conductive material include conductive fine particles and conductive polymers.

  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 can be obtained. Most preferred is polyethylene dioxythiophene.

  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 (abbreviated as PEDOT / PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is H.264. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series.

  The content of the functional material in the linear liquid 2 applied on the substrate 1 is preferably in the range of 0.01% by weight to 1% by weight with respect to the total amount of the linear liquid 2. The content rate is a value before being dried immediately after the line-shaped liquid 2 is applied on the substrate 1. When the content of the functional material is in the range of 0.01% by weight or more and 1% by weight or less, the fine line formation due to the coffee stain phenomenon is further stabilized.

  As the liquid containing the functional material, 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.

  Further, the liquid containing the functional material may contain various additives such as a surfactant as long as the effects of the present invention are not impaired. By using a surfactant, for example, when the line-like liquid 2 is formed on the substrate 1 using a droplet discharge device, the surface tension is adjusted to stabilize the discharge, etc. Is possible. 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 modified with polyether. For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. ing. The content of the surfactant is preferably 1% by weight or less with respect to the total amount of the line liquid 2.

  The substrate to which the liquid containing the functional material is applied 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 alloys), ceramics, and the like can be used. 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.

  Next, the shape of the thin wire unit 3 will be described with reference to FIG.

  FIG. 17 is a perspective view schematically showing a thin line unit formed on a substrate. A part of the thin line unit 3 composed of the inner thin line 31 and the outer thin line 32 is shown, and is merely shown in a straight line for convenience. Further, the thin wire unit 3 described here is the one immediately after being formed by the coffee stain phenomenon. As described above, the shape and the like of the fine wire unit 3 can be changed by post-processing such as plating or partial removal of the fine wire.

  The range of the arrangement interval I between the inner thin wire 31 and the outer thin wire 32 is not particularly limited. For example, the inner thin wire 31 and the outer thin wire 32 are preferably in the range of 10 μm to 1000 μm, more preferably in the range of 10 μm to 500 μm. The most preferable range is 300 μm or less. The arrangement interval I between the inner thin wire 31 and the outer thin wire 32 is the distance between the inner thin wire 31 and the outer thin wire 32 immediately after being formed by the coffee stain phenomenon (the state in which no post-processing such as plating or partial removal of the thin wire is performed). It is the distance between each maximum protrusion part, and is determined corresponding to the line width of the line-shaped liquid provided on the base material 1. It is preferable to reduce the line width of the line liquid and to reduce the arrangement interval I. This reduces the drying load, stabilizes the formation of the inner thin wire 31 and the outer thin wire 32, and further shortens the tact time. Even in the case where the arrangement interval I is reduced in this way, as described above, a part of the thin line composed of the inner thin line 31 and the outer thin line 32 can be easily removed, so that the desired arrangement interval can be freely set for the remaining thin lines without being removed. Can be set high. By using such partial removal of the thin wires, for example, 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, or 1 mm while maintaining the stable formation of the inner thin wire 31 and the outer thin wire 32. A large arrangement interval as described above can be easily set.

  The inner fine line 31 and the outer fine line 32 constituting the fine line unit 3 do not necessarily have to be island shapes completely independent from each other. As illustrated, the inner thin wire 31 and the outer thin wire 32 are formed between the inner thin wire 31 and the outer thin wire 32 by the thin film portion 30 formed at a height lower than the height of the inner thin wire 31 and the outer thin wire 32. It is also preferred that it be formed as a connected continuum. The height Z of the thinnest portion where the thickness of the functional material is the thinnest between the inner thin wire 31 and the outer thin wire 32, specifically, the height Z of the thinnest portion of the thin film portion 30 is in the range of 10 nm or less. Is preferred. Most preferably, the thin film portion 30 is provided in the range of 0 <Z ≦ 10 nm in order to achieve a balance between transparency and stability. Even when a conductive material is used as the functional material, the thin film portion 30 has a very high resistance and is substantially an insulator. Therefore, the inner thin wire 31 and the outer thin wire 32 connected via the thin film portion 30 are , Become electrically insulated. Therefore, the selective electrolytic plating described above can be suitably performed.

  The line widths W1 and W2 of the inner thin wire 31 and the outer thin wire 32 of the thin wire unit 3 are each preferably 10 μm or less. If it is 10 micrometers or less, since it will be a level which cannot be visually recognized normally, it is more preferable from a viewpoint of improving transparency. Considering the stability of the inner thin wire 31 and the outer thin wire 32, the line widths W1 and W2 are preferably in the range of 2 μm or more and 10 μm or less, respectively. The widths W1 and W2 of the inner thin wire 31 and the outer thin wire 32 are the height of the thinnest portion where the thickness of the functional material is the thinnest between the inner thin wire 31 and the outer thin wire 32, and the Z When the projecting heights of the inner thin wire 31 and the outer thin wire 32 from Y1 and Y2 are Y1, Y2, the width of the inner thin wire 31 and the outer thin wire 32 at half the height of Y1 and Y2. For example, when the thin wire unit 3 has the thin film portion 30 described above, the height of the thinnest portion in the thin film portion 30 can be set to Z. When the height of the thinnest portion of the functional material between the inner thin wire 31 and the outer thin wire 32 is 0, the line widths W1 and W2 of the inner thin wire 31 and the outer thin wire 32 are the inner side from the surface of the substrate 1. The widths of the inner thin line 31 and the outer thin line 32 at half the heights H1 and H2 of the thin line 31 and the outer thin line 32 are used.

  Since the line widths W1 and W2 of the inner thin wire 31 and the outer thin wire 32 constituting the thin wire unit 3 are extremely thin as described above, from the viewpoint of securing a cross-sectional area and reducing resistance, It is desirable that the heights H1 and H2 of the inner thin wire 31 and the outer thin wire 32 be higher. Specifically, the heights H1 and H2 of the inner fine wire 31 and the outer fine wire 32 are preferably in the range of 50 nm to 5 μm. Furthermore, from the viewpoint of improving the stability of the thin wire unit 3, the H1 / W1 ratio and the H2 / W2 ratio are preferably in the range of 0.01 or more and 1 or less, respectively.

  Furthermore, in order to further improve the thinning of the thin wire unit 3, the H1 / Z ratio and the H2 / Z ratio are each preferably 5 or more, more preferably 10 or more, and preferably 20 or more. Particularly preferred.

  As described above, the description of the thin line unit 3 can be applied to the thin line unit 5 and a thin line unit additionally provided.

  The functional material included in the thin wire is preferably a conductive material as described above. By using a conductive material, a pattern formed of the aggregate of thin wires can be suitably used as a transparent conductive film (also referred to as an electrode film or a transparent electrode).

  Although the use of the substrate with a transparent conductive film is not particularly limited, it can be used for various devices included in various electronic apparatuses. From the viewpoint of remarkably exhibiting the effects of the present invention, for example, as a transparent electrode for displays of various systems such as liquid crystal, plasma, organic electroluminescence, field emission, etc., or as a touch panel, 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. It is particularly preferable to use a substrate with a transparent conductive film as a touch panel sensor for electronic devices such as smartphones and tablet terminals. When used as a touch panel sensor, it is preferable to use the above-described thin line pattern as the transparent conductive film (X electrode and Y electrode) on both sides of the transparent substrate.

  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.

1. Formation of pattern (Example 1); Formation of functional fine line pattern (1) <Ink composition>
An ink (liquid containing a functional material) having the following composition was prepared.
Silver nanoparticles (average particle size: 20 nm): 0.23% by weight
Surfactant (manufactured by Big Chemie “BYK348”): 0.05 wt%
Diethylene glycol monobutyl ether (abbreviation: DEGBE) (dispersion medium): 20% by weight
・ Water (dispersion medium): remaining amount

<Base material>
As a base material, a PET base material that was surface-treated so that the contact angle of a liquid containing a functional material was 20.3 ° was prepared. As the surface treatment, corona discharge treatment was performed using “PS-1M” manufactured by Shinko Electric Instrumentation Co., Ltd.

<Patterning>
Ink was ejected from the inkjet head while moving the inkjet head (Konica Minolta “KM1024iLHE-30” (standard droplet volume 30 pL)) relative to the substrate, as shown in FIG. A plurality of closed geometric figures having an inner edge and an outer edge were formed on the substrate by the first linear liquid 2 containing the functional material. The geometric figure is a quadrangle whose sides are inclined at 45 ° with respect to the longitudinal direction of the substrate.

  By drying the first line-shaped liquid 2, the functional material is selectively deposited on the inner edge 21 and the outer edge 22 of the first line-shaped liquid 2, as shown in FIG. A plurality of first fine line units 3 each including the inner fine line 31 and the outer fine line 32 were formed. The inner thin wire 31 and the outer thin wire 32 of each obtained first thin wire unit 3 are quadrangles whose sides are inclined at 45 ° with respect to the longitudinal direction of the substrate. In this quadrangle, the length of one side measured along the middle line between the inner thin wire 31 and the outer thin wire 32 is 0.75 mm.

  Next, ink is ejected from the inkjet head while moving the inkjet head relative to the substrate, and as shown in FIG. 4A, the second linear liquid 4 containing a functional material is formed on the substrate. To form a plurality of closed geometric figures having inner and outer edges. The geometric figure is a quadrangle whose sides are inclined at 45 ° with respect to the longitudinal direction of the substrate. The formation position of the second line-shaped liquid 4 was set so that the vicinity of the quadrangular vertex of the second line-shaped liquid 4 covered the quadrangular vertex of the outer fine line 32 of the first fine-line unit 3 previously formed.

  By drying the second line-shaped liquid 4, the functional material is selectively deposited on the inner edge 41 and the outer edge 42 of the second line-shaped liquid 4, as shown in FIG. 4B. A plurality of second fine line units 5 each including the inner fine line 51 and the outer fine line 52 were formed. The inner thin wires 51 and the outer thin wires 52 of the obtained second thin wire units 5 are quadrangles whose sides are inclined at 45 ° with respect to the longitudinal direction of the base material. In this quadrangle, the length of one side measured along the middle line between the inner thin line 51 and the outer thin line 52 is 0.75 mm.

  The outer fine wire 32 of the first fine wire unit 3 and the outer fine wire 52 of the second fine wire unit 5 are connected to each other, and the inner fine wire 31 of the first fine wire unit 3 and the inner fine wire 51 of the second fine wire unit 5 are mutually connected. Not connected and independent.

  In the above process, the drying of the line-shaped liquid is promoted by patterning the line-shaped liquid on the substrate disposed on the stage heated to 70 ° C. Further, the formed thin wire was baked for 10 minutes in an oven at 130 ° C.

  An optical micrograph of the fine line pattern (1) thus obtained is shown in FIG. It can be seen from the photograph shown in FIG. 18 that a plurality of fine line units each formed of an inner fine line and an outer fine line are formed.

(Example 2); Formation of functional fine wire pattern (2) Copper electrolytic plating selectively on outer fine wires 32 and 52 of fine wire units 3 and 5 constituting functional fine wire pattern (1) obtained in Example 1 As a result, a functional thin line pattern (2) similar to that shown in FIG. 6 was obtained. Copper electrolytic plating was performed under the following plating conditions.

<Plating conditions>
Electric power was fed from the conductive surface of the substrate on which the functional fine wire pattern (1) of Example 1 cut to 70 × 140 mm was formed, and electrolytic plating was performed in the following plating bath. The anode was connected to a copper plate for plating, and the substrate was placed at a position 30 mm away from the copper plate in the plating bath. Plating was performed at a constant current of 0.2 A for 1 minute. After the completion of plating, the substrate was washed with water and dried.

<Plating bath>
20 g of copper sulfate pentahydrate, 1.3 g of 1N hydrochloric acid, and 5 g of a gloss-imparting agent (“ST901C” manufactured by Meltex) were prepared with ion-exchanged water so as to be 1000 mL.

  An optical micrograph of the functional fine line pattern (2) thus obtained is shown in FIG. From the photograph shown in FIG. 19, it can be seen that the outer thin wires electrically connected to each other were selectively plated (here, copper plating). Note that the photograph shown in FIG. 19 is a gray scale, but in the color photograph, it can be confirmed that the copper-plated outer fine wire is colored copper.

(Example 3); Formation of functional fine line pattern (3) The outer fine lines 32 and 52 constituting the functional fine line pattern (2) obtained in Example 2 are selectively subjected to nickel electrolytic plating and a plating solution. By removing the inner thin wires 31, 51, a functional fine wire pattern (3) similar to that shown in FIG. 7 was obtained. Nickel electrolytic plating was performed under the following plating conditions.

<Plating conditions>
Power was supplied from the conductive surface of the base material on which the functional thin wire pattern (2) of Example 2 was formed, and electrolytic plating was performed in the following plating bath. The anode was connected to a nickel plate for plating, and the substrate was placed at a position 30 mm away from the nickel plate in the plating bath. Plating was performed at a constant current of 0.2 A for 30 seconds. In order to sufficiently remove the inner fine wires 31 and 51 with the plating solution, after the plating was completed, the substrate was left in the plating bath for 10 minutes, then washed with water and dried.

<Plating bath>
240 g of nickel sulfate, 45 g of nickel chloride, and 30 g of boric acid were prepared with ion-exchanged water so as to be 1000 mL.

  An optical micrograph of the functional fine line pattern (3) thus obtained is shown in FIG. From the photograph shown in FIG. 20, it can be seen that the outer thin wires 32 and 52 electrically connected to each other are selectively plated (in this case, nickel plating). Note that the photograph shown in FIG. 20 is a gray scale, but in the color photograph, it can be confirmed that the outer fine line has changed from copper color to colorless (silver color by nickel). It can also be seen that the inner thin lines 31 and 51 are selectively removed.

2. Evaluation Method (1) Fine Line Width The fine line width [μm] is a value measured by observing the line width of the outer fine line constituting the fine line unit with a microscope.

(2) Transmittance The transmittance [%] is the total light transmittance [%] measured using AUTOMATIC HAZEMETER (MODEL TC-H III DP) manufactured by Tokyo Denshoku. In addition, it corrected using the base material (film) without a pattern, and measured it as the total light transmittance of the created pattern.

(3) Sheet resistance value The sheet resistance value [Ω / □] is a value measured using a Loresta EP (MODEL MCP-T360 type) series 4-probe probe (ESP) manufactured by Dia Instruments.

(4) Low visibility The sample was visually observed from a position 50 cm away on the light table, and it was evaluated that the low visibility was so excellent that the fine line could not be visually recognized. Specifically, the evaluation was performed according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is more than B evaluation, it can use preferably in the use as a transparent conductive film.

<Evaluation criteria>
A: Fine line is not visible B: Fine line is slightly visible C: Fine line is clearly visible (not applicable)

  The results are shown in Table 1.

3. Evaluation In Examples 1 to 3, a fine line pattern could be stably formed with a high degree of freedom by using a fine line unit comprising an inner fine line and a functional outer material.

  From the results of Examples 2 and 3 in Table 1, it can be seen that the sheet resistance value can be more suitably reduced by plating the outer fine wire of the fine wire unit. In addition, it can be seen from the results of Example 3 that the transmittance and the low visibility can be improved more appropriately by removing the inner fine line of the fine line unit and increasing the arrangement interval of the fine lines.

1: Substrate 2: First line-shaped liquid 20: Area to which liquid is not applied 21: Inner edge 22: Outer edge 3: First fine line unit 31: Inner fine line 32: Outer fine line 4: Second line-shaped liquid 40: Liquid 41: inner edge 42: outer edge 5: second fine wire unit 51: inner fine wire 52: outer fine wire

Claims (10)

On the base material, a plurality of polygonal fine wires containing functional materials are arranged two-dimensionally,
A functional thin line pattern, wherein at least one pair of polygonal thin lines are connected at two intersections by intersecting both sides sandwiching the vertex of the polygon.   2. The functional fine line pattern according to claim 1, wherein an overlapping area of the internal regions of the polygonal thin lines connected to each other is 1/10 or less of an area of the internal region of each polygonal thin line.   The functional thin line pattern according to claim 1 or 2, wherein the polygonal thin line is a triangle, a quadrangle, a hexagon or an octagon.   A plurality of the thin polygonal wires that are quadrangles whose sides are inclined with respect to the longitudinal direction of the base material are arranged in parallel at a predetermined pitch in each of the longitudinal direction and the width direction of the base material. The functional thin line pattern according to claim 3.   The functional thin line pattern according to claim 1, wherein the functional material is a conductive material.   The functional fine line pattern according to claim 1, wherein the polygonal fine lines are covered with a plating layer.   The functional thin line pattern according to claim 1, wherein the functional thin line pattern is provided on both surfaces of the base material.   The said functional material is an electroconductive material, It has a transparent conductive film which consists of a functional fine wire pattern in any one of Claims 1-7 in a base material surface, The base material with a transparent conductive film characterized by the above-mentioned.   A device comprising the substrate with a transparent conductive film according to claim 8.   An electronic apparatus comprising the device according to claim 9.