JP6515928B2 - Method of forming mesh-like functional pattern, mesh-like functional pattern and functional substrate - Google Patents

Description

  The present invention relates to a method of forming a mesh-like functional pattern, a mesh-like functional pattern formed by the method, and a functional substrate provided with the mesh-like functional pattern.

  Conventionally, a method using photolithography has been widely used as a method of forming a fine line pattern containing a functional material. However, since photolithography technology has a lot of loss of materials and the process becomes complicated, a method that can improve these is considered.

  For example, there is a method in which a thin line pattern is formed by continuously applying droplets containing a functional material to a substrate by an inkjet method or the like. However, in the ordinary inkjet method, the width of the thin line can not be made equal to or less than the diameter of the discharged droplet, and a thin line pattern with a line width of several μm can not be formed.

  As an approach of fine line formation by the ink jet method, after a repellent is applied to the whole surface in advance, a part of the repellent is hydrophilized by laser etc. to form a lyophilic pattern, and the droplets are given thereto by the ink jet There is a method of forming a thin line. However, this method has a problem that the process becomes complicated when a repellent is applied or a lyophilic pattern is formed by a laser.

  On the other hand, there is known a method of forming functional patterns, which are solid content in droplets, utilizing convection inside the droplets on the periphery of the droplets to form a pattern having a width smaller than that of the droplets. (Patent Document 1). According to this method, it is possible to form a thin wire having a width of several μm equal to or less than the diameter of the droplet without requiring a special process.

  Further, Patent Document 2 describes that a transparent conductive film is formed by forming a ring of a fine width of conductive fine particles and connecting a plurality of the rings by using this method.

  However, in these methods, there are problems in that the number of intersections of the rings increases to create a conductive path, and the transparency is degraded.

  On the other hand, the applicant has separated the conductive material in the liquid applied in the form of a line into the edges by the movement of the liquid to form a parallel line pattern, and further, it is transparent comprising the parallel line pattern. It has been invented and reported to form a conductive film (Patent Document 3).

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

  Patent Document 3 describes that, when forming parallel line patterns crossed in a grid shape, one-pass printing is used to double the ink application amount at the intersections, but in this case, the intersections are formed. Is a ring that is thicker than the parallel line part, and such a ring part may be viewed periodically, and there is room for further improvement in low visibility (that is, a property that is difficult to see).

  Thus, the applicant further studies to apply a first line of liquid in one direction, drying it to form a first parallel line pattern and then crossing it with a second direction in a different direction. The present inventors have attempted to form a mesh-like functional pattern in which parallel line patterns in different directions cross each other by applying a line-like liquid and drying to form a second parallel line pattern.

  However, since the distance between the lines constituting the second parallel line pattern is different between the inside and outside of the first parallel line pattern formation area, expansion or narrowing of the lines occurs, resulting in low visibility. A new problem has been found to be reduced.

  Further, particularly in the case where the functional material is a conductive material, due to the above-mentioned swelling or narrowing that occurs in the second parallel line pattern, the length of the conductive path is in a direction along the first parallel line pattern, and New problems have also been found that they differ in the direction along the parallel line pattern and cause variations in resistance.

  Therefore, an object of the present invention is to provide a mesh-like functional pattern formation method, a mesh-like functional pattern, and a functional base material that can improve low visibility and can suppress variations in resistance.

  Further, other objects of the present invention will become clear by the following description.

  The above problems are solved by the following inventions.

1.
The functional material is selectively deposited on the edge in the process of applying a first line-like liquid containing the functional material on a substrate and drying the first line-like liquid to obtain the functional material Form a first parallel line pattern composed of two line segments including
Next, a second line-like liquid containing a functional material is applied on the substrate so as to cross the formation region of the first parallel line pattern, and the second line-like liquid is dried in the process of drying the second line-like liquid. By selectively depositing functional material on the edge to form a second parallel line pattern composed of two segments containing the functional material,
When forming a mesh-like functional pattern in which the first parallel line pattern and the second parallel line pattern intersect,
With respect to the interval between the two lines constituting the second parallel line pattern, an average interval A in the formation area of the first parallel line pattern and an average outside the formation area of the first parallel line pattern The formation method of the mesh-like functional pattern adjusted so that the space | interval B may satisfy following formula (1).
0.9 ≦ B / A ≦ 1.1 (1)

2.
As adjustment for satisfying the equation (1), the difference between the surface energy in the formation region of the first parallel line pattern and the surface energy outside the formation region of the first parallel line pattern is 5 mN / m. The formation method of the mesh-like functional pattern of said 1 made into the following.

3.
As adjustment for satisfying the equation (1), the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-like liquid, and outside the formation region of the first parallel line pattern The method for forming a mesh-like functional pattern according to the above 1, wherein the difference between the surface energy and the surface energy is 5 mN / m or less.

4.
As adjustment for satisfying the equation (1), the contact angle of the second line-like liquid in the formation area of the first parallel line pattern, and the second angle outside the formation area of the first parallel line pattern The method for forming a mesh-like functional pattern according to the above-mentioned 1, wherein the difference with the contact angle of the line-like liquid of 2 is 10 ° or less.

5.
As adjustment for satisfying the formula (1), the contact angle of the second linear liquid on the solid surface obtained by applying and drying the functional material contained in the first linear liquid, and the first The method for forming a mesh-like functional pattern according to the above 1, wherein the difference with the contact angle of the second linear liquid outside the formation area of the parallel line pattern is 10 ° or less.

6.
As adjustment for satisfying the equation (1), the amount of liquid application per length of the second line-like liquid in the formation area of the first parallel line pattern, and the formation of the first parallel line pattern The method for forming a mesh-like functional pattern according to the above 1, wherein the liquid application amount per length of the second linear liquid outside the region is made different.

7.
As the adjustment for satisfying the equation (1), after forming the first parallel line pattern, before applying the second line-like liquid, including within the formation area of the first parallel line pattern 5. The method for forming a mesh-like functional pattern according to the above 1, wherein the region is cleaned.

8.
The mesh-like functional pattern according to 7 above, wherein the washing is performed by washing one or two or more selected from washing by heating, washing by electromagnetic waves, washing by solvent, washing by gas, and washing by plasma. Formation method.

9.
The method for forming a mesh-like functional pattern according to any one of 1 to 8, wherein the functional material is a conductive material.

10.
The mesh-like functional pattern formed by the formation method of the mesh-like functional pattern in any one of said 1-9.

11.
10. A functional substrate provided with the mesh-like functional pattern according to 10 above.

Schematic explanatory drawing which illustrates notionally an example of the method of forming a parallel line pattern Explanatory drawing explaining an example (reference example) of the formation method of a mesh-like functional pattern Explanatory drawing explaining the other example (reference example) of the formation method of a mesh-like functional pattern Explanatory drawing explaining the other example of the formation method of a mesh-like functional pattern Principal part enlarged view showing an example of formation of intersection X A diagram for explaining an example of a method of measuring the average interval A and the average interval B A partial enlarged plan view showing an example of a parallel line pattern formed on a substrate Explanatory drawing explaining the (viii)-(viii) line cross section in FIG. 7 Optical micrograph of mesh-like functional pattern (Example) Optical micrograph of mesh-like functional pattern (Reference example)

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  In the present invention, as a basic principle, when drying a liquid containing a functional material applied on a substrate, the phenomenon of selectively depositing the functional material contained in the liquid on the edge of the liquid is used can do. This phenomenon may also be referred to as a coffee ring phenomenon or a coffee stain phenomenon. The present invention is not limited to the formation of a ring-shaped pattern, so in the following description, this phenomenon may be referred to as a coffee stain phenomenon.

  FIG. 1 is a schematic explanatory view conceptually illustrating an example of a method of forming a parallel line pattern using such a basic principle.

  In FIG. 1, 1 is a substrate, 2 is a line-like liquid containing a functional material, and 3 is formed by selectively depositing a functional material on the edge of the line-like liquid 2 It is a coating film (Hereafter, it may be called parallel line pattern.). Further, 7 is a applying means for applying a liquid onto the substrate 1, and here, it is constituted by a droplet discharge device. The droplet discharge device 7 can be configured by, for example, an ink jet head included in an ink jet recording device.

  As shown in FIG. 1A, while the droplet discharge device 7 and the base material 1 are relatively scanned, the liquid droplet discharge device 7 discharges a liquid containing a functional material, and a plurality of discharges are sequentially performed. The droplets coalesce on the substrate to form a linear liquid 2 containing the functional material.

  Then, as shown in FIG. 1 (b), when evaporating the line liquid 2 and drying it, a functional material is selectively deposited on the edge of the line liquid 2 by using the coffee stain phenomenon.

  The coffee stain phenomenon can be caused by setting conditions for drying the line-like liquid 2.

  That is, the drying of the line liquid 2 disposed on the substrate 1 is quicker at the edge compared to the central part, and the solid concentration reaches the saturation concentration with the progress of drying, and the solid content at the edge of the line liquid 2 Precipitation occurs. By the precipitated solid content, the edge of the line-like liquid 2 is fixed, and the contraction in the width direction of the line-like liquid 2 accompanying the subsequent drying is suppressed. Due to this effect, the liquid in the line liquid 2 forms a convection from the center to the edge so as to compensate for the liquid lost by evaporation at the edge. Since the convection is caused by the fixation of the contact line of the line liquid 2 and the difference in evaporation between the center part of the line liquid 2 and the edge due to drying, the solid concentration, the contact between the line liquid 2 and the substrate 1 It can be controlled by adjusting and adjusting according to the amount of horn, linear liquid 2, heating temperature of base material 1, arrangement density of linear liquid 2, or environmental factors of temperature, humidity and pressure. .

  As a result, as shown in FIG. 1C, a parallel line pattern 3 consisting of thin lines containing a functional material is formed on the base material 1. The parallel line pattern 3 formed from one linear liquid 2 is constituted by one set of two thin lines 31 and 32.

  By applying the method of forming parallel line patterns as described above, it is possible to form a mesh-like functional pattern formed by intersecting a plurality of parallel line patterns.

  Such a mesh-like functional pattern is advantageous for realizing distribution of the functional material on the substrate while maintaining low visibility.

  In particular, the line segments constituting the parallel line pattern formed as described above can realize a line width of several μm, and the mesh-like functional pattern is a functional material itself by the fine line width. Even if it is not transparent, it is not recognized by human eyes and looks as transparent.

  The shape of the fine line pattern of the functional material can be set by the device using the functional material. As an example of a device, a touch sensor used for a touch panel uses a transparent surface electrode to detect a position by a finger or the like.

  If a conductive material is used as the functional material in the mesh-like functional pattern, it can be preferably applied to a transparent surface electrode or the like for a touch panel or the like. From the viewpoint of forming a plane electrode or the like, meshing with a plurality of parallel line patterns different in forming direction from each other is very effective in increasing the number of conductive paths.

  As a method of forming such a mesh-like functional pattern, the following method may be mentioned.

  FIG. 2 is an explanatory view for explaining an example (reference example) of a method of forming a mesh-like functional pattern.

  First, as shown in FIG. 2A, the line-like liquid 2 is applied in a mesh shape on the base material 1. That is, the linear liquid 2 is applied so as to intersect at the intersection X.

  Then, by drying the line-like liquid 2, as shown in FIG. 2B, it is possible to form a mesh-like pattern by the parallel line pattern 3.

  At this time, as a result of the functional material contained in the linear liquid 2 being deposited on the edge, the line segments 31 and 32 are broken at the intersection X where parallel lines in different directions intersect.

  As a method of preventing the disconnection of the line segments 31 and 32 at the intersection X, the following method may be mentioned.

  FIG. 3 is an explanatory view for explaining another example (reference example) of the method of forming the mesh-like functional pattern.

  In this example, in the method shown in FIG. 2, as shown in FIG. 3A, the amount of ink in the portion of the intersection formed by the linear liquid 2 is set larger than in the other portions.

  According to this method, as shown in FIG. 3B, disconnection of the line segments 31 and 32 at the intersection X can be prevented in the mesh pattern by the parallel line pattern 3.

  At this time, since the ink amount to the intersection X is increased, as shown in FIG. 3B, the intersection X has a ring shape having a diameter larger than the distance between the line segments 31 and 32.

  The generation of such a ring-shaped portion is advantageous from the viewpoint of preventing disconnection of the line segments 31 and 32, for example, making it easy to ensure conductivity, but such a ring-shaped portion is periodically viewed In some cases, it has been found that there is a limit in terms of further improving low visibility.

  Further, as a method of preventing disconnection of the line segments 31 and 32 at the intersection portion X, the following method may also be mentioned.

  FIG. 4 is an explanatory view for explaining still another example of the method of forming the mesh-like functional pattern.

  First, as shown in FIG. 4A, the linear liquid 2 is applied in a first direction (left and right direction in the drawing).

  In the process of drying the line liquid 2, the functional material is selectively deposited on the edge to form a first parallel line pattern 3 as shown in FIG. 4 (b).

  Then, as shown in FIG. 4C, a second direction different from the first direction (in this example, a direction perpendicular to the first direction and in the vertical direction in the drawing) Apply 2 line liquid 4 That is, the second linear liquid 4 is applied so as to intersect with the formation area of the first parallel line pattern 3.

  In the process of drying the line liquid 4, the functional material is selectively deposited on the edge to form a second parallel line pattern 5 as shown in FIG. 4 (d). Reference numerals 51 and 52 denote line segments constituting the second parallel line pattern 5.

  As described above, the mesh-like functional pattern is formed by the first parallel line pattern 3 and the second parallel line pattern 5 which are different from each other in the formation direction.

  According to this method, it is possible to prevent disconnection of the line segments 31 and 32 and the line segments 51 and 52 at the intersection X where parallel lines in different directions cross each other.

  FIG. 5 is an enlarged view of an essential part showing an example of forming the intersection X. As shown in FIG. 5 (a) and 5 (b) are reference examples, and FIG. 5 (c) is a view for explaining the present invention.

  That is, in the example described with reference to FIG. 4, as shown in FIGS. 5A and 5B, at the intersection X, between the line segments 51 and 52 forming the second parallel line pattern, Swelling (Fig. 5 (a)) and narrowing (Fig. 5 (b)) occur.

  It has been found that the swelling and narrowing between the line segments 51 and 52 cause the limit to the improvement of the low visibility.

  In addition, particularly when the functional material is a conductive material, due to such swelling or narrowing, the direction of the conductive path along the first parallel line pattern 3 (first direction) and the second parallel line It differs in the direction along the pattern 5 (the second direction), and it has been found that there is room for further improvement from the viewpoint of preventing variations in resistance.

  In order to improve these, in the example described with reference to FIG. 4, as shown in FIG. 5 (c), with regard to the distance between the two line segments 51 and 52 constituting the second parallel line pattern 5, The average spacing A in the formation area of the first parallel line pattern 3 and the average spacing B outside the formation area of the first parallel line pattern 3 are adjusted to satisfy the following formula (1).

  0.9 ≦ B / A ≦ 1.1 (1)

  Thereby, in the obtained mesh-like functional pattern, the disconnection of the line segment can be prevented and the low visibility can be improved. In particular, when the functional material is a conductive material, the length of the conductive path is The same effects can be obtained with high precision in the first direction and the second direction, and the effect of being able to preferably suppress the variation in resistance can be obtained.

  The formation area of the first parallel line pattern 3 can be referred to as an area from one line segment 31 to the other line segment 32 constituting the first parallel line pattern, and in another viewpoint, the first parallel line pattern 3 It can also be referred to as the application area of the first line-like liquid 2 applied to form the line pattern 3.

  With respect to the distance between the line segments 51 and 52 constituting the second parallel line pattern 5, the average distance A in the formation area of the first parallel line pattern 3 and the average outside the formation area of the first parallel line pattern 3 The interval B can be an average value of the intervals measured at a plurality of points.

  The measurement locations at a plurality of locations (n locations) set to measure the average interval A may be equally spaced along the second direction in the formation region of the first parallel line pattern 3 preferable. In addition, a plurality of (m locations) of measurement points set to measure the average distance B should be arranged at equal intervals along the second direction outside the formation area of the first parallel line pattern 3 Is preferred.

  Specifically, it is preferable to measure the average interval A and the average interval B as follows.

  FIG. 6 is a diagram for explaining an example of a method of measuring the average interval A and the average interval B.

First, as shown in FIG. 6, the average interval A is along the line segments 31 and 32 forming the first parallel line pattern for the intervals between the line segments 51 and 52 forming the second parallel line pattern 5. It can be determined as the average of the intervals measured at a total of seven places A _{1 to} A ₇ of two places A ₁ and A ₂ and five places A _{3 to} A ₇ inside the line segments 31 and 32. At this time, the total of seven measurement points A _{1 to} A ₇ are positioned at equal intervals along the forming direction (second direction) of the second parallel line pattern.

On the other hand, as shown in FIG. 6, the average interval B is a total of seven measurement locations A ₁ to 7 pertaining to the above-described average interval A for the interval between the line segments 51 and 52 constituting the second parallel line pattern 5. it can be determined as the average of the measured intervals in the measurement points B ₁ .about.B ₅ of total 5 points adjacent to a _7. At this time, a total of seven measurement points A pertaining to the above-mentioned average interval A are taken along the forming direction (second direction) of the second parallel line pattern at these five measurement points B _{1 to} B ₅ in total. it can be positioned in the same regular intervals as ₁ ~A _7. A total of seven measurement locations A _{1 to} A ₇ pertaining to the measurement of the average interval A and a total of five measurement locations B _{1 to} B ₅ pertaining to the measurement of the average interval B are equally spaced along the second direction. Can be positioned at

In the illustrated example, an example is shown in which the measurement points B _{1 to} B ₅ of the average interval B are set adjacent to the lower side in the figure with respect to the measurement points A _{1 to} A ₇ of the average interval A. In the figure, it can also be set adjacent to the upper side. At this time, the measurement locations B _{1 to} B ₅ of the average interval B are set on either the upper side (one side) or the lower side (the other side) so that the difference between the average interval A and the average interval B becomes larger. It is preferable to do.

In the example of FIG. 6, although the case where two places A ₁ and A ₂ along the line segments 31 and 32 constituting the first parallel line pattern are included as the measurement points for the average interval A has been described, , 32 may be included. In addition, the locations along the line segments 31 and 32 may not be included.

In the example of FIG. 6, the case where five measurement points A _{3 to} A ₇ inside the line segments 31 and 32 constituting the first parallel line pattern are included as measurement points for the average interval A is described. It is not necessary to be 5 places, and it is preferable that it is 2 or more multiple places.

In the example of FIG. 6, as the measurement locations for the average distance B, than the line segment 31 and 32 constituting the first pattern of parallel lines has been described comprising five points B ₁ .about.B ₅ outer necessarily It is not necessary to be 5 places, and it is preferable that it is 2 or more multiple places.

  The distance between the line segments 51 and 52 constituting the second parallel line pattern 5 measured at each measurement point to obtain the average distance A and the average distance B can be defined as follows.

  FIG. 7 is a partially enlarged plan view showing an example of a parallel line pattern formed on a substrate. FIG. 8 is an explanatory view for explaining the (viii)-(viii) line cross section in FIG. 7, and a cross section obtained by cutting one set of two thin lines included in the pattern in a direction orthogonal to the line segment direction Face) is explained.

  The distance I between the line segments 51 and 52 constituting the second parallel line pattern 5 can be defined as the distance between the maximum projections of the line segments 51 and 52 as shown in FIG. Therefore, the average interval A and the average interval B can be determined by measuring the interval I at each measurement point described above.

  It may be said that the adjustment to satisfy the above-mentioned equation (1) is to adjust one or more of the factors that may affect the ratio B / A of the average interval A and the average interval B. Such factors are not particularly limited, and can be selected as appropriate.

  The following can be illustrated as a preferable aspect of adjustment for satisfy | filling Formula (1) mentioned above.

  In the first aspect, as adjustment for satisfying the above-mentioned equation (1), the surface energy in the formation region of the first parallel line pattern 3 and the surface energy outside the formation region of the first parallel line pattern 3 Make the difference 5 mN / m or less.

  Here, the surface energy in the formation area of the first parallel line pattern 3 can be the surface energy measured in the central area between the line segments 31 and 32 constituting the first parallel line pattern. Alternatively, as an alternative method, the surface energy in the formation area of the first parallel line pattern 3 is prepared separately as a substrate similar to the substrate 1, and the first linear liquid 2 and the substrate 2 are formed on the substrate. After 20 μL of the same liquid is dropped and dried under the same conditions as drying of the first linear liquid 2, the surface energy measured in the central region of the dried film can also be obtained.

  On the other hand, the surface energy outside the formation area of the first parallel line pattern 3 is the surface energy of the base material 1 in the area where the first linear liquid 2 for forming the first parallel line pattern 3 was not applied. It can be done.

  The surface energy can be calculated from the Young-Fowkes equation.

  By setting the difference in the surface energy to 5 mN / m or less, the change in the wettability to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3, The above-mentioned formula (1) can be preferably satisfied.

  When the surface energy in the formation region of the first parallel line pattern 3 is larger than the outside of the formation region, the second line liquid 4 is spread by wetting if the difference in surface energy exceeds 5 mN / m. In the parallel line pattern 5 of this, it causes the bulge between the line segments 51 and 52.

  On the other hand, when the surface energy in the formation area of the first parallel line pattern 3 is smaller than that outside the formation area, the line segment 51 in the second parallel line pattern 5 when the difference in surface energy exceeds 5 mN / m. , Cause narrowing between 52.

  The means for adjusting the surface energy difference between the inside and the outside of the formation area of the first parallel line pattern 3 is not particularly limited, but for example, a method of surface treating a region including the outside of the formation area of the first parallel line pattern 3; The method of changing the liquid composition of the 1st line-like liquid 2 etc. is preferable.

  As a method of performing surface treatment on a region including the outside of the formation region of the first parallel line pattern 3, surface treatment for changing the surface energy of the substrate 1 is performed before forming the first parallel line pattern 3. You can list the method of applying. The surface treatment may be performed only on the area outside the formation area of the first parallel line pattern 3 or on the area including the outside of the formation area and the inside of the formation area. It is also preferable to surface-treat the entire surface of the substrate 1.

  In the case of changing the liquid composition of the first line-like liquid 2, it can be performed by selection of blending components (functional materials, additives, solvents and the like), adjustment of blending amounts of the respective components, and the like.

  In the second embodiment, the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-like liquid 2 and the first parallel line as adjustment for satisfying the above-mentioned equation (1) The difference with the surface energy outside the formation area of the pattern 3 is 5 mN / m or less.

  The “solid surface” is the surface of a solid film obtained by applying and drying the functional material contained in the first line-like liquid 2 on any substrate, and the surface energy of the substrate itself and It refers to the surface of a solid film coated with the substrate such that the contact angle does not affect the surface energy and the contact angle on the surface of the solid film. The application of the functional material can be performed, for example, by applying a coating solution containing the functional material. A liquid having the same composition as the first line-like liquid 2 may be used as a coating liquid for forming a solid surface.

  Of the formation area of the first parallel line pattern 3, the area between the line segments 31 and 32 is in the first line-like liquid 2 which has not been transported to the position of the line segments 31 and 32 due to the coffee stain phenomenon. Some components may remain slightly. Such residual components may cause the spacing between the line segments 51 and 52 constituting the second parallel line pattern 5 to be nonuniform.

  At this time, the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-like liquid 2 is an index for realizing more reliable adjustment to satisfy the above-mentioned equation (1). obtain. That is, even if a large amount of residual components exist in the region between the line segments 31 and 32, it is less likely to affect the interval between the line segments 51 and 52 beyond the influence of the solid surface. Therefore, the reliability can be further improved by adjusting based on the difference between the surface energy of the solid surface and the surface energy outside the formation region of the first parallel line pattern 3.

  When the surface energy of the solid surface is larger than the outside of the formation area of the first parallel line pattern 3 and the difference in surface energy exceeds 5 mN / m, the second line liquid 4 is spread due to the wetting and spreading. In the parallel line pattern 5, it causes a bulge between the line segments 51 and 52.

  On the other hand, when the surface energy of the solid surface is smaller than the outside of the formation area of the first parallel line pattern 3, if the difference in surface energy exceeds 5 mN / m, the line segment 51 in the second parallel line pattern 5; It causes narrowing between 52.

  The means for adjusting the surface energy of the solid surface and the surface energy difference outside the formation region of the first parallel line pattern 3 is not particularly limited, and the means described in regard to the first aspect can be preferably used.

  In the third aspect, the contact angle of the second line-like liquid 4 in the formation region of the first parallel line pattern 3 and the first parallel line pattern 3 as adjustment for satisfying the above-mentioned equation (1). The difference with the contact angle of the second linear liquid 4 outside the formation region is 10 ° or less.

  Here, the contact angle in the formation area of the first parallel line pattern 3 can be a contact angle measured in the central area between the line segments 31 and 32 constituting the first parallel line pattern. Alternatively, as an alternative method, the contact angle in the formation region of the first parallel line pattern 3 is prepared separately as a substrate similar to the substrate 1, and the first linear liquid 2 and the substrate 2 are formed on the substrate. After 20 μL of the same liquid is dropped and dried under the same conditions as drying of the first linear liquid 2, the contact angle measured in the central region of the dried membrane can also be obtained.

  On the other hand, the contact angle outside the formation area of the first parallel line pattern 3 is the same as that on the substrate 1 in the area where the first line liquid 2 for forming the first parallel line pattern 3 was not applied. It can be a contact angle.

  The contact angle can be measured using a contact angle measurement device DM-501 manufactured by Kyowa Interface Chemicals Co., Ltd. In the third embodiment, the contact angle is set to a value 5 seconds after dropping a liquid having the same composition as the second linear liquid 4.

  By setting the difference in the contact angle to 10 ° or less, it is possible to reduce the change in the wettability to the second linear liquid 4 inside and outside the formation region of the first parallel line pattern 3, and the second In the parallel line pattern 5, the interval between the line segments 51 and 52 can be made to satisfy the above-mentioned equation (1).

  When the contact angle in the formation area of the first parallel line pattern is larger than the contact angle outside the formation area, the second line liquid 4 is spread by wetting when the difference in the contact angle exceeds 10 °. In the formation area of the parallel line pattern 3 of 1, the distance between the line segments 51 and 52 of the second parallel line pattern 5 becomes larger than the outside of the formation area, resulting in an expanded shape.

  On the other hand, if the contact angle in the formation region of the first parallel line pattern is smaller than the contact angle outside the formation region, the difference in the contact angle exceeds 10 °, the inside of the formation region of the first parallel line pattern 3 In this case, the distance between the line segments 51 and 52 of the second parallel line pattern 5 becomes smaller than the outside of the formation region, and becomes a narrowed shape.

  The means for adjusting the contact angle difference is not particularly limited, and the means described as the means for adjusting the surface energy difference in the first embodiment can be preferably used. Furthermore, the liquid composition of the second linear liquid 4 can also be changed as a means for adjusting the difference in the contact angle. When changing the liquid composition of the 2nd line-like liquid 4, it can carry out by selection of a combination ingredient (a functional material, an additive, a solvent, etc.), adjustment of a compounding quantity of each ingredient, etc. It is also preferable to make the liquid of the second linear liquid 4 different from the liquid of the first linear liquid 2.

  In the fourth aspect, as adjustment for satisfying the above-mentioned equation (1), the contact of the second linear liquid 4 on the solid surface obtained by applying and drying the functional material contained in the first linear liquid 2 The difference between the angle and the contact angle of the second linear liquid 4 outside the formation area of the first parallel line pattern 3 is 10 ° or less. Here, the description in the second mode is incorporated for "solid surface".

  By setting the difference in the contact angle to 10 ° or less, it is possible to reduce the change in the wettability to the second linear liquid 4 inside and outside the formation region of the first parallel line pattern 3, and the second In the parallel line pattern 5, the interval between the line segments 51 and 52 can be made to satisfy the above-mentioned equation (1).

  In the same manner as described above for the surface energy in the second aspect, the reliability can be further improved by adjusting the contact angle on the solid surface as an index.

  When the contact angle on the solid surface is larger than the contact angle outside the formation area of the first parallel line pattern 3, if the difference in the contact angle exceeds 10 °, the second line liquid 4 wets and spreads, In the formation area of the parallel line pattern 3 of 1, the distance between the line segments 51 and 52 of the second parallel line pattern 5 becomes larger than the outside of the formation area, resulting in an expanded shape.

  On the other hand, if the contact angle on the solid surface is smaller than the contact angle outside the formation area of the first parallel line pattern 3, if the difference in contact angle exceeds 10 °, within the formation area of the first parallel line pattern 3 In this case, the distance between the line segments 51 and 52 of the second parallel line pattern 5 becomes smaller than the outside of the formation region, and becomes a narrowed shape.

  The means for adjusting the difference between the contact angle on the solid surface and the contact angle outside the formation area of the first parallel line pattern 3 is not particularly limited, and the means described in regard to the third aspect can be preferably used.

  In the fifth aspect, the contact angle of the solvent having the highest boiling point among the solvents in the second linear liquid 4 outside the formation region of the first parallel line pattern 3 as adjustment for satisfying the above-mentioned equation (1) Below 6 °.

  Here, the contact angle outside the formation area of the first parallel line pattern 3 is on the base material 1 in the area where the first linear liquid 2 for forming the first parallel line pattern 3 was not applied. The contact angle of

  The contact angle can be measured using a contact angle measurement device DM-501 manufactured by Kyowa Interface Chemicals Co., Ltd. In the fifth aspect, the contact angle is set to a value 5 seconds after dropping the solvent having the highest boiling point among the solvents in the second line-like liquid 4.

  By setting the contact angle to 6 ° or less, the change in the wettability to the second linear liquid 4 can be reduced inside and outside the formation area of the first parallel line pattern 3, and the second parallel line In the pattern 5, the interval between the line segments 51 and 52 can be made to satisfy the above-mentioned equation (1).

  The means for adjusting the contact angle is not particularly limited, and the means described as the means for adjusting the surface energy difference in the first embodiment can be preferably used.

  In the sixth aspect, as adjustment for satisfying the above-mentioned equation (1), the liquid application amount per length of the second linear liquid 4 in the formation region of the first parallel line pattern 3, and the first The amount of applied liquid per length of the second linear liquid 4 outside the formation area of the parallel line pattern 3 is made different.

  For example, in the case where the wettability of the second line liquid 4 is better in the formation area than in the formation area of the first parallel line pattern 3, the length per second linear liquid 4 in the formation area is The amount of liquid applied is relatively reduced relative to the outside of the formation area.

  Further, for example, when the wettability of the second line liquid 4 is good outside the formation area of the first parallel line pattern 3 outside the formation area, the length of the second line liquid 4 in the formation area The amount of liquid applied per unit is relatively increased outside the formation area.

  In this manner, in the formation area of the first parallel line pattern 3, the distance between the line segments 51 and 52 of the second parallel line pattern 5 is prevented from expanding or narrowing more than outside the formation area. Ru.

  The difference in the liquid application amount between the inside and the outside of the formation area of the first parallel line pattern 3 can be appropriately adjusted so as to satisfy the formula (1). For example, when the inkjet method is used to form the second line-like liquid 4, the number of droplets ejected per unit length of the second line-like liquid 4, the droplet volume per one drop, The difference in the liquid application amount can be set by making the inside and outside of the formation region of the parallel line pattern 3 different.

  In the seventh aspect, as the adjustment to satisfy the above-mentioned equation (1), after forming the first parallel line pattern 3, before applying the second line-like liquid 4, the first parallel line pattern 3 is formed. The area including the formation area of is washed.

  As described above, in the area where the first parallel line pattern 3 is formed, the area between the line segments 31 and 32 does not carry up to the position of the line segments 31 and 32 due to the coffee stain phenomenon. Some components in the liquid 2 may remain slightly. Such residual components may cause the spacing between the line segments 51 and 52 constituting the second parallel line pattern 5 to be nonuniform.

  Washing can also be said to remove such residual components. At this time, how much the remaining component is removed is affected by the washing conditions, for example, the setting of the type and strength of washing. Using this relationship, it is possible to eliminate the difference in the wettability of the second line-like liquid 4 inside and outside the formation area of the first parallel line pattern 3. In one aspect, the cleaning is performed by removing residual components so that at least the distance between the line segments 51 and 52 forming the second parallel line pattern 5 can achieve that the above-mentioned equation (1) is satisfied. possible. In this sense, cleaning can be positioned as an example of adjustment to satisfy the above-mentioned equation (1).

  The cleaning may be performed only in the formation area of the first parallel line pattern, or may be performed on the area including the formation area and the outside of the formation area of the first parallel line pattern. It is also preferable to wash the entire surface of the substrate 1.

  When the cleaning is performed only in the formation region of the first parallel line pattern, for example, irradiation with an electromagnetic wave or the like is performed in a state where the outside of the formation region is masked, or the cleaning solvent is selectively selected using an inkjet method. It becomes possible by providing in a formation area.

  The method of washing is not particularly limited, and, for example, the washing method usually used in industrial products can be used. For example, it is preferable to perform one or a combination of two or more selected from cleaning by heating, cleaning by electromagnetic waves, cleaning by solvent, cleaning by gas, and cleaning by plasma.

  As a cleaning method by heating, there are a continuous heating method by an infrared heater, an oven, a hot plate or the like, and an instantaneous heating method by a xenon flash lamp or the like. The heating conditions (temperature, time) and the like are appropriately set in such a range that the distance between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described equation (1). In the case where the substrate 1 is a film or the like, it is preferable to set in the range where the substrate 1 is not deformed. From this point of view, a method using a xenon flash lamp which heats instantaneously and in particular causes less damage to a substrate such as a film is preferable.

  As the electromagnetic wave, a method of irradiating an electron beam, a gamma ray, an ultraviolet ray or the like can be used. The irradiation condition of the electromagnetic wave is appropriately set in such a range that the distance between the line segments 51 and 52 forming the parallel line pattern 5 satisfies the above-mentioned equation (1).

  The solvent used for the cleaning with the solvent is not limited as long as it can satisfy the above-mentioned formula (1), but it is possible to select one having little influence on the parallel line pattern formed by the deposition of the functional material. preferable. A solvent suitable for washing can be appropriately selected according to the type of functional material. For example, in the case of water dispersion type silver nanoparticles, alcohol solvents and the like are suitable.

  The conditions for cleaning by plasma can be set as appropriate such that the distance between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described equation (1).

  Hereinafter, with reference to FIG. 7 and FIG. 8 again, a preferable example of the dimension of the parallel line pattern constituting the mesh-like functional pattern will be described. Here, the second parallel line pattern 5 will be mainly described, but the first parallel line pattern 3 can be described in the same manner.

  The interval I between the line segments 51 and 52 constituting the parallel line pattern 5 can be defined as the distance between the respective maximum projections of the line segments 51 and 52 as described above, and preferably 10 μm to 300 μm. It is preferable to be adjusted to the range.

  The pair of thin lines (line segments) 51 and 52 of the parallel line pattern 5 need not necessarily be islands completely independent of each other. As illustrated, the two line segments 51, 52 are connected by a thin film portion 50 formed between the line segments 51, 52 at a height lower than the height of the line segments 51, 52. It is also preferred that it be formed as a continuous body.

  The line widths W1 and W2 of the line segments 51 and 52 of the parallel line pattern 5 are preferably 10 μm or less. If it is 10 μm or less, the level is usually not visible, which is more preferable from the viewpoint of improving the transparency. In consideration of the stability of each of the line segments 51 and 52, the line widths W1 and W2 of each of the line segments 51 and 52 are preferably in the range of 2 μm to 10 μm.

  In addition, with the widths W1 and W2 of the line segments 51 and 52, the height of the thinnest portion at which the thickness of the functional material is the thinnest between the line segments 51 and 52 is Z, and the line segment from Z When the projecting heights of 51 and 52 are Y1 and Y2, they are defined as the widths of the line segments 51 and 52 at half the height of Y1 and Y2. For example, when the parallel line pattern 5 has the thin film portion 50 described above, the height of the thinnest portion of the thin film portion 50 can be set to Z. When the height of the thinnest portion of the functional material between the line segments 51 and 52 is 0, the line widths W1 and W2 of the line segments 51 and 52 are line segments 51 and 52 from the surface of the base material 1. Is defined as the width of the line segments 51 and 52 at half the heights h1 and h2.

  Since the line widths W1 and W2 of the line segments 51 and 52 constituting the parallel line pattern 5 can be extremely thin, the line segments from the surface of the base material 1 in terms of securing a cross-sectional area and reducing resistance The heights h1 and h2 of 51 and 52 are preferably high. Specifically, the heights h1 and h2 of the line segments 51 and 52 are preferably in the range of 50 nm to 5 μm.

  Furthermore, from the viewpoint of improving the stability of the parallel line pattern 5, the h1 / W1 ratio and the h2 / W2 ratio are each preferably in the range of 0.01 or more and 1 or less.

  Further, from the viewpoint of further improving the thinning of the parallel line pattern 5, the height Z of the thinnest portion where the thickness of the functional material is the thinnest between the line segments 51 and 52, specifically, the maximum thickness of the thin film portion 50. The height Z of the thin portion is preferably in the range of 10 nm or less. Most preferably, the thin film portion 50 is provided in the range of 0 <Z ≦ 10 nm in order to balance the transparency and the stability.

  Furthermore, to further improve the thinning of the parallel line pattern 5, the h1 / Z ratio and the h2 / Z ratio are each preferably 5 or more, more preferably 10 or more, and 20 or more. Is particularly preferred.

  Furthermore, it is preferable to give similar shapes (similar cross-sectional areas) to the line segments 51 and 52, and more specifically, the heights h1 and h2 of the line segments 51 and 52 are substantially It is preferable to set the same value. Similarly, the line widths W1 and W2 of the line segment 51 and the line segment 52 are preferably set to substantially the same value.

  The line segments 51 and 52 do not necessarily have to be parallel, and it is sufficient if the line segments 51 and 52 are not connected over at least a certain length L in the line segment direction. Preferably, the line segments 51 and 52 are substantially parallel over at least a certain length L in the line segment direction.

  The length L in the line segment direction of the line segments 51 and 52 is preferably five times or more of the interval I of the line segments 51 and 52, and more preferably ten times or more. The length L and the interval I can be set corresponding to the formation length and the formation width of the linear liquid 4 for forming the parallel line pattern line 5.

  It is also preferable that the line segments 51 and 52 be connected at a formation start point and an end point (a start point and an end point across a certain length L of the line segment direction) of the linear liquid 4 and be formed as a continuous body.

  The line segments 51 and 52 preferably have substantially equal line widths W1 and W2, and the line widths W1 and W2 are preferably sufficiently smaller than the distance between two lines (interval I).

  Furthermore, it is preferable that the line segment 51 and the line segment 52 which comprise the parallel line pattern 5 produced | generated from one linear liquid be formed simultaneously.

  As for parallel line pattern 5, it is especially preferred that each line segment 51 and 52 fulfills all the conditions of following (a)-(e).

  (A) When the heights of the line segments 51 and 52 are h1 and h2 and the height of the thinnest portion in each line is Z, 5 ≦ h1 / Z and 5 ≦ h2 / Z.

  (A) W1 ≦ 10 μm and W2 ≦ 10 μm, where W1 and W2 are the widths of the line segments 51 and 52, respectively.

  (C) Assuming that a distance between the line segments 51 and 52 is I, 10 μm ≦ I ≦ 300 μm.

  (D) Assuming that the heights of the line segments 51 and 52 are h1 and h2, 50 nm <h1 <5 μm and 50 nm <h2 <5 μm.

  The base material on which the mesh-like functional pattern is to be formed is not particularly limited. For example, glass, plastic (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyethylene, polypropylene, acrylic) , Polyester, polyamide, etc., metal (copper, nickel, aluminum, iron, etc., or alloy), ceramic, etc., which may be used alone or in a bonded state. . Among them, plastic is preferable, and polyethylene terephthalate, and polyolefin such as polyethylene and polypropylene are preferable. In particular, PET, PEN, etc. which are easy to bond are preferably used. The easy adhesion process is a process of modifying the surface of the substrate to improve the adhesiveness, and it is also preferable to apply this as a surface treatment for changing the surface energy and the contact angle described above.

  The functional material contained in the linear liquid is not particularly limited as long as it is a material for imparting a specific function to the substrate. Providing a specific function means, for example, using a conductive material as a functional material in the case of imparting conductivity to a substrate, and also providing an insulating property in the case of imparting insulating properties. We say to use as material. Preferred examples of the functional material include conductive fine particles, conductive materials such as conductive polymers, insulating materials, semiconductor materials, optical filter materials, dielectric materials and the like. In particular, conductive materials such as conductive fine particles, conductive polymers, or conductive material precursors can be preferably exemplified as functional materials in using a transparent conductive film. The conductive material precursor refers to one that can be changed to a conductive material by performing appropriate processing.

  The conductive 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 of In, etc. can be preferably exemplified. Among them, metal fine particles such as Au, Ag and Cu are more preferable because they can form a circuit pattern having low electric resistance and resistance to 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.

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

  The conductive polymer is not particularly limited, but preferably includes a π-conjugated conductive polymer.

  The π-conjugated conductive polymer is not particularly limited, and polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, polyparaphenylenevinylenes, poly Chain-like conductive polymers such as paraphenylene sulfides, polyazulenes, polyisothianaphthenes, and polythiazyl can be used. Among them, polythiophenes and polyanilines are preferable in that high conductivity can be obtained. It is most preferred that it is polyethylenedioxythiophene.

  The conductive polymer is more preferably composed of the π-conjugated conductive polymer described above and a polyanion. Such a conductive polymer can be easily produced by chemical oxidation polymerization of a precursor monomer forming a π-conjugated conductive polymer in the presence of a polyanion with an appropriate oxidizing agent and an oxidation catalyst.

  The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester and a copolymer thereof, which is an anion It consists of a structural unit having a group and a structural unit not having an anion group.

  This polyanion is a solubilizing polymer that solubilizes a π-conjugated conductive polymer in a solvent. In addition, the anion group of the polyanion functions as a dopant for the π conjugated conductive polymer to improve the conductivity and heat resistance of the π conjugated conductive polymer.

  As the anion group of the polyanion, any functional group capable of causing chemical oxidation doping to the π-conjugated conductive polymer can be used, but among them, from the viewpoint of the easiness of production and stability, a monosubstituted sulfate ester group, Mono-substituted phosphoric acid ester group, phosphoric acid group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group to the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, polyisoprene sulfone Acids, polyvinyl carboxylic acids, polystyrene carboxylic acids, polyallyl carboxylic acids, polyacrylic carboxylic acids, polymethacrylic carboxylic acids, poly-2-acrylamido-2-methylpropane carboxylic acids, polyisoprene carboxylic acids, polyacrylic acids, etc. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  In addition, it may be a polyanion having F (fluorine atom) in the compound. Specifically, "Nafion" (manufactured by Dupont) containing a perfluorosulfonic acid group, "Flemion" (manufactured by Asahi Glass Co., Ltd.) made of a perfluoro type vinyl ether containing a carboxylic acid group, and the like can be mentioned.

  Among these, a compound having a sulfonic acid is more preferable because the liquid ejection stability is particularly good when using an inkjet printing method, and high conductivity can be obtained.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and poly acrylic acid butyl sulfonic acid are preferable. These polyanions have the effect of being excellent in conductivity.

  The polymerization degree of the polyanion is preferably in the range of 10 to 100000 monomer units, and in the light of solvent solubility and conductivity, the range of 50 to 10000 is more preferable.

  Commercially available materials can also be preferably used as the conductive polymer. For example, a conductive polymer consisting of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (abbreviated as PEDOT / PSS) is disclosed in H. C. It is commercially available from Starck as "CLEVIOS" series, from Aldrich as "PEDOT-PASS 483095, 560598", and from Nagase Chemtex as "Denatron" series. Also, polyaniline is commercially available from Nissan Chemical Co., Ltd. as "ORMECON" series.

  Further, as a functional material particularly in the use of a transparent conductive film, a conductive material precursor can also be preferably used. For example, an organic metal complex, an inorganic metal salt, an electroless plating catalyst, etc. can be preferably exemplified.

  As the liquid containing the functional material, one or more of water, an organic solvent and the like can be used in combination.

  The organic solvent is not particularly limited but, for example, isopropanol, 1-butanol, 2-butanol, 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4- Examples thereof include alcohols such as butanediol and propylene glycol, and ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether.

  When a plurality of solvents are used in combination, the drying of the liquid proceeds in the order of the boiling points of the solvents, so the solvent with the highest boiling point remains at the end. For this reason, the wettability of the solvent having the highest boiling point to the substrate is related to the appearance of the coffee stain phenomenon.

  Moreover, as a liquid containing a functional material, various additives, such as surfactant, may be included in the range which does not impair the effect of the present invention.

  It is also preferable to adjust the contact angle with the substrate by using a surfactant to preferably cause the above-mentioned coffee stain phenomenon. The surfactant is not particularly limited, but a silicon surfactant or the like can be used. The silicone surfactant is a polyether-modified side chain or terminal of dimethylpolysiloxy acid, for example, "KF-351A" or "KF-642" manufactured by Shin-Etsu Chemical Co., Ltd. or "BYK347" manufactured by Big Chemie , "BYK 348" and the like are commercially available. The addition amount of the surfactant is preferably 1% by weight or less based on the total amount of the liquid containing the functional material.

  The method for applying the line-like liquid on the substrate is not particularly limited, as long as the line-like liquid can be applied in a flowability sufficient to cause a coffee stain phenomenon, various methods may be used. It can be used. As a particularly preferable method, for example, a dispenser method, an inkjet method and the like can be mentioned.

  The mesh-like functional pattern of the present invention may be obtained by further post-processing the mesh-like functional pattern obtained as described above. Post-processing can further enhance the functionality. Although post-processing is not particularly limited, for example, plating and the like can be mentioned. It is preferable that, for example, the reflectance be reduced by plating.

  The functional substrate of the present invention comprises the mesh-like functional pattern described above. In particular, the functional material is preferably a substrate with a transparent conductive film formed by imparting conductivity to a coating film made of a mesh-like functional pattern.

  The conductivity is imparted to the coating film, for example, by using a conductive material as a functional material, or post treatment is performed on a coating film formed using a conductive material precursor as a functional material. It can be carried out by imparting conductivity by application.

  The functional base material has a pattern shape in which the reflected light of the thin line portion constituting the coating film is widely distributed, glare is reduced, and it is difficult to be recognized even in a bright environment, that is, low visibility can be improved.

  The application of the functional substrate is not particularly limited, and can be used for various devices included in various electronic devices.

  Since a functional base material is excellent in low visibility of a thin line which constitutes a coat, a remarkable effect is exhibited in a use where a user looks at a picture through the base material.

  Particularly preferred applications of the substrate with a transparent conductive film are, for example, as transparent electrodes for displays of various systems such as liquid crystal, plasma, organic electroluminescence, field emission, and the like, from the viewpoint of achieving the effects of the present invention significantly. It can be suitably used as a transparent electrode used for mobile phones, electronic paper, various solar cells, various electroluminescent light control devices and the like.

  More specifically, a substrate with a transparent conductive film is suitably used as a transparent electrode of the device. The device is not particularly limited but, for example, a touch panel sensor can be preferably exemplified. Moreover, although it is not limited especially as an electronic device provided with these devices, For example, a smart phone, a tablet terminal etc. can be illustrated preferably.

  The configuration described for one aspect in the above description can be appropriately applied to the other aspects.

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

Example 1
1. Preparation of Ink An ink 1 having the following composition was prepared.
Aqueous dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight): 1.75% by weight
・ Silicone-based surfactant ("BYK-348" manufactured by Bick Chemie): 0.01 wt%
・ Pure water: Remainder

2. Preparation of a base material As a base material, the base material 1 which consists of a PET base material which made surface energy E of a base material 52 mN / m by easy adhesion processing (surface treatment) was used.

3. Measurement of Surface Energy and Contact Angle Before forming the mesh-like functional pattern, the surface energy in the formation area of the first parallel line pattern formed by the ink 1 and the contact angle of the second line-like liquid The measurement was performed by a substitute method.

(1) Measurement of Surface Energy 20 μL of the ink 1 was dropped on the substrate 1 and dried to form a ring-shaped fine wire around the droplet by a coffee ring phenomenon. Thereafter, the contact angles of water, propylene carbonate and diiodomethane with respect to the central region inside the ring-like thin wire were measured, and the surface energy was calculated from the Young-Fowkes equation. Here, the contact angles of water, propylene carbonate and diiodomethane were measured using a contact angle measuring apparatus "DM-501" manufactured by Kyowa Interface Chemical Co., Ltd. (the same apparatus is used for measuring the contact angles described below) It was. The calculated surface energy value was 56 mN / m. This value is the surface energy C in the formation area of the first parallel line pattern.

(2) Measurement of contact angle of second linear liquid a. Measurement of the contact angle of the second linear liquid in the formation area of the first parallel line pattern 20 μL of the ink 1 is dropped onto the easily adherent polyethylene terephthalate (PET) substrate having a contact angle of 22 ° to the ink 1 Then, it was dried to form a ring-like thin line by the coffee ring phenomenon around the droplet. Thereafter, the contact angle of the ink 1 (the same composition as the second linear liquid) with respect to the central region inside the ring-like thin wire was measured. The contact angle measured was 17 °. This value is taken as the contact angle F of the second linear liquid in the formation area of the first parallel line pattern.

B. Measurement of the Contact Angle of the Second Line-Like Liquid Outside the Formation Area of the First Parallel Line Pattern 3 μL of the ink 1 was dropped on the substrate surface, and the contact angle of the second line-like liquid on the substrate surface was measured . The contact angle measured was 20 °. This value is taken as the contact angle G of the second linear liquid outside the formation area of the first parallel line pattern.

4. Formation of pattern Using an XY robot (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.) and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) using an ink jet head “512 LHX” (standard droplet volume 42 pL) manufactured by Konica Minolta The ink 1 is sequentially discharged onto the substrate 1 as droplets so as to have a pitch of 282 μm in the nozzle row direction and a pitch of 45 μm in the scanning direction, and the droplets applied continuously in the scanning direction on the substrate are united. Thus, a plurality of linear liquids were formed. During printing, the stage on which the substrate is placed is heated at 70 ° C., and in the process of drying these line-like liquids, solid content is deposited on the peripheral part, so one pair of line-like liquids is used. Parallel line patterns were formed.

  Thereafter, the substrate is rotated by 90 °, and a plurality of second line-like liquids of ink 1 are applied in the same manner as described above in the direction perpendicular to the first parallel line pattern, and dried. Two parallel line patterns were formed.

  Thus, a mesh-like functional pattern was formed in which the first parallel line pattern and the second parallel line pattern intersect at right angles. The size of the entire mesh-like functional pattern is 50 mm × 50 mm.

(Example 2)
1. Preparation of Ink An ink 2 having the following composition was prepared.
Aqueous dispersion 2 of silver nanoparticles (silver nanoparticles: 40% by weight): 1.75% by weight
・ Silicone-based surfactant ("BYK-348" manufactured by Bick Chemie): 0.01 wt%
・ Pure water: Remainder

  The aqueous dispersion 2 of silver nanoparticles differs from the aqueous dispersion 1 of silver nanoparticles used in Example 1 in the dispersant.

2. Preparation of Substrate A substrate 1 (surface energy E = 52 mN / m) was used as a substrate.

3. Measurement of Surface Energy and Contact Angle As a result of measurement in the same manner as in Example 1 except that Ink 1 of Example 1 is replaced with Ink 2, the surface energy C in the formation region of the first parallel line pattern is 49 mN / m. The contact angle F of the second linear liquid in the formation region of the first parallel line pattern is 25 °, and the contact angle G of the second linear liquid outside the formation region of the first parallel line pattern is , 21 °.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 1 except that Ink 1 was changed to Ink 2.

(Example 3)
1. Preparation of Ink Ink 1 was used as an ink.

2. Preparation of Substrate A substrate 2 made of a PET substrate having a surface energy of 48 mN / m by easy adhesion processing (surface treatment) was used as the substrate.

3. Measurement of Surface Energy and Contact Angle As a result of measurement in the same manner as in Example 1 except that the base material 1 of Example 1 is replaced with the base material 2, the surface energy C in the formation region of the first parallel line pattern is 56 mN / m And the contact angle F of the second linear liquid in the formation region of the first parallel line pattern is 17 °, and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern G was 28 °.

4. Formation of pattern Using an XY robot (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.) and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) using an ink jet head “512 LHX” (standard droplet volume 42 pL) manufactured by Konica Minolta The ink 1 is sequentially discharged onto the substrate 2 as droplets so as to have a pitch of 282 μm in the nozzle row direction and a pitch of 45 μm in the scanning direction, and the droplets continuously applied in the scanning direction on the substrate are united. Thus, a plurality of linear liquids were formed. During printing, the stage on which the substrate is placed is heated at 70 ° C., and in the process of drying these line-like liquids, solid content is deposited on the peripheral part, so one pair of line-like liquids is used. Parallel line patterns were formed.

  Thereafter, the substrate on which the first parallel line pattern was formed was placed on a hot plate at 120 ° C., and was washed by heating for 1 hour.

  After washing by heating, the substrate is rotated by 90 °, and a plurality of second linear liquids of ink 1 are applied in the same manner as described above in the direction perpendicular to the first parallel line pattern and dried. To form a second parallel line pattern.

  Thus, a mesh-like functional pattern was formed in which the first parallel line pattern and the second parallel line pattern intersect at right angles. The size of the entire mesh-like functional pattern is 50 mm × 50 mm.

(Example 4)
In Example 3, a mesh-like pattern was formed in the same manner as in Example 3 except that cleaning by heating was changed to cleaning by electromagnetic waves described below.

Cleaning by electromagnetic waves
Cleaning with a xenon flash lamp was performed as cleaning with electromagnetic waves.
Using a xenon flash lamp device “SINTERON 2000” manufactured by Xenon, a xenon flash is irradiated once with a pulse width of 500 μs and an applied voltage of 3.8 kV to clean the area including the area where the first parallel line pattern is formed did.

(Example 5)
In Example 3, a mesh-like pattern was formed in the same manner as in Example 3 except that cleaning by heating was changed to cleaning with the following solvent.

<Cleaning with solvent>
By immersing in 2-propanol for 10 minutes, the area including the area where the first parallel line pattern was formed was cleaned.

(Example 6)
1. Preparation of Ink Ink 1 was used as an ink.

2. Preparation of Substrate A substrate 2 (surface energy E = 48 mN / m) was used as a substrate.

3. Measurement of Surface Energy and Contact Angle As a result of measurement in the same manner as in Example 1 except that the base material 1 of Example 1 is replaced with the base material 2, the surface energy C in the formation region of the first parallel line pattern is 56 mN / m And the contact angle F of the second linear liquid in the formation region of the first parallel line pattern is 17 °, and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern G was 28 °.

4. Formation of pattern Using an XY robot (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.) and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) using an ink jet head “512 LHX” (standard droplet volume 42 pL) manufactured by Konica Minolta The ink 1 is sequentially discharged onto the substrate 2 as droplets so as to have a pitch of 282 μm in the nozzle row direction and a pitch of 45 μm in the scanning direction, and the droplets continuously applied in the scanning direction on the substrate are united. Thus, a plurality of linear liquids were formed. During printing, the stage on which the substrate is placed is heated at 70 ° C., and in the process of drying these line-like liquids, solid content is deposited on the peripheral part, so one pair of line-like liquids is used. Parallel thin line patterns were formed.

  Thereafter, the substrate is rotated by 90 °, and a plurality of second line-like liquids of ink 1 are applied in a direction perpendicular to the first parallel line pattern, and dried to form a second parallel line pattern. It formed. At this time, when applying the ink, the amount of applied liquid per length of the second linear liquid in the area where the first parallel line pattern is formed is the amount of liquid applied outside the area where the first parallel line pattern is formed. It adjusted to 70% and applied.

  Thus, a mesh-like functional pattern was formed in which the first parallel line pattern and the second parallel line pattern intersect at right angles. The size of the entire mesh-like functional pattern is 50 mm × 50 mm.

(Example 7)
1. Preparation of Ink Ink 1 was used as an ink.

2. Preparation of Substrate A substrate 3 composed of a PET substrate having a surface energy E of 56 mN / m by easy adhesion processing (surface treatment) was used as the substrate.

3. Measurement of Surface Energy and Contact Angle First, a water dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight) is applied to a substrate 3 with a wire bar # 7 and dried to obtain a functional material (silver The solid surface of the nanoparticles) was prepared. The surface energy of this solid surface was measured to be 61 mN / m. This value was taken as the surface energy D of the solid surface formed by applying and drying a liquid having the same composition as the first linear liquid.

  Moreover, as a result of replacing the base material 1 of Example 1 with the base material 3 and measuring in the same manner as in Example 1, the surface energy C in the formation region of the first parallel line pattern is 56 mN / m. The contact angle F of the second linear liquid in the formation region of the parallel line pattern is 15 °, and the contact angle G of the second linear liquid outside the formation region of the first parallel line pattern is 19 ° Met.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 1 except that the base material 1 was replaced with the base material 3 in Example 1.

(Example 8)
1. Preparation of Ink An ink 4 having the following composition was prepared.
Aqueous dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight): 1.75% by weight
-Diethylene glycol monobutyl ether: 20% by weight
・ Pure water: Remainder

2. Preparation of Substrate A substrate 1 (surface energy E = 52 mN / m) was used as a substrate.

3. Measurement of Contact Angle The contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C.) outside the formation region of the first parallel line pattern was measured using a contact angle measurement device “DM-501” manufactured by Kyowa Interface Chemicals Co., Ltd. The angle H was 5 °. In addition, it was set as the value 5 second after dripping diethylene glycol monobutyl ether.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 1 except that Ink 1 was replaced with Ink 4 in Example 1.

(Comparative example 1)
1. Preparation of Ink Ink 1 was used as an ink.

2. Preparation of Substrate A substrate 2 (surface energy E = 48 mN / m) was used as a substrate.

3. Measurement of Surface Energy and Contact Angle As a result of measurement in the same manner as in Example 1 except that the base material 1 of Example 1 is replaced with the base material 2, the surface energy C in the formation region of the first parallel line pattern is 56 mN / m And the contact angle F of the second linear liquid in the formation region of the first parallel line pattern is 17 °, and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern G was 28 °.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 1 except that the base material 1 was replaced with the base material 2 in Example 1.

(Comparative example 2)
1. Preparation of Ink An ink 3 having the following composition was prepared.
Aqueous dispersion 3 of silver nanoparticles (silver nanoparticles: 40% by weight): 1.75% by weight
・ Silicone-based surfactant ("BYK-348" manufactured by Bick Chemie): 0.01 wt%
・ Pure water: Remainder

  The aqueous dispersion 3 of silver nanoparticles is different from the aqueous dispersions 1 and 2 of silver nanoparticles in the dispersing agent.

2. Preparation of Substrate A substrate 2 (surface energy E = 48 mN / m) was used as a substrate.

3. Measurement of Surface Energy and Contact Angle As a result of measuring in the same manner as in Example 1 by replacing Ink 1 of Example 1 with Ink 3 and further replacing Base 1 with Base 2, the formation region of the first parallel line pattern The surface energy C inside is 61 mN / m, and the contact angle F of the second linear liquid in the formation region of the first parallel line pattern is 12 °, and outside the formation region of the first parallel line pattern The contact angle G of the second linear liquid was 29 °.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 1 except that the ink 1 was replaced with the ink 3 and the base material 1 was replaced with the base material 2 in Example 1.

(Comparative example 3)
1. Preparation of Ink Ink 4 was used as an ink.

2. Preparation of Substrate A substrate 2 (surface energy E = 48 mN / m) was used as a substrate.

3. Measurement of Contact Angle The contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C.) outside the formation region of the first parallel line pattern was measured using a contact angle measurement device “DM-501” manufactured by Kyowa Interface Chemicals Co., Ltd. The angle H was 8 °. In addition, it was set as the value 5 second after dripping diethylene glycol monobutyl ether.

4. Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 8 except that the base material 1 was replaced with the base material 2 in Example 8.

<Measurement of Average Interval A and Average Interval B>
In the mesh-like functional patterns obtained in Examples 1 to 7 and Comparative Examples 1 and 2, the formation region of the first parallel line pattern for the interval between two lines constituting the second parallel line pattern the average distance a in the inner, was calculated as the mean value of the measured intervals in the measurement point a ₁ to a ₇ of a total of 7 points described in FIG. Also, for the interval between two lines constituting the second parallel line pattern, the average interval B outside the formation area of the first parallel line pattern is a total of five measurement points B ₁ to 5 described in FIG. It was calculated as the mean value of the measured intervals in B _5. Furthermore, the value of B / A in the above-mentioned equation (1) was determined from the values of the average interval A and the average interval B.

  By obtaining the value of B / A, it can be determined whether the above-mentioned equation (1) is satisfied. That is, it can be said that it can be determined whether or not the adjustment for satisfying the above-mentioned equation (1) has been achieved.

<Evaluation method>
Evaluation Method of Low Visibility The mesh-like functional patterns obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were visually observed and evaluated according to the following evaluation criteria.

[Evaluation criteria]
A: It looks like a periodic pattern is not visible and looks uniform throughout B: A periodic pattern is visible

Evaluation Method of Directional Unevenness in Resistance Value With respect to the mesh-like functional patterns obtained in Examples 1 to 7 and Comparative Examples 1 and 2, the directional unevenness in resistance value was evaluated by the following method.

  A strip 50 mm long and 10 mm wide is cut out parallel to the direction of the first parallel line pattern (first direction), and electrodes for measurement with silver paste are attached to both ends of the long side (ie short side). The resistance of was measured by a tester. Similarly, the resistance between the terminals is measured with a tester even in a strip 50 mm long and 10 mm wide parallel to the direction (second direction) of the second parallel line pattern, and resistance in the first direction and the second direction The ratio of Specifically, the ratio of resistance is 100 as a value obtained by dividing the absolute value of the difference between “resistance in the second direction” and “resistance in the first direction” by “resistance in the first direction”. It is shown in fractions.

  As a certain standard, it is practically preferable that the ratio of resistance is 10% or less, and it can be evaluated that it is practically undesirable if the ratio of resistance exceeds 10%.

  The above results are shown in Table 1.

<Evaluation>
From Table 1, in Examples 1 to 8 in which the average interval A and the average interval B are adjusted so as to satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1”, excellent in low visibility, It can be seen that the directional unevenness of the resistance value can be prevented. On the other hand, in Comparative Examples 1 to 3 in which such adjustment was not performed, it is understood that low visibility is inferior and it is not possible to sufficiently prevent directional unevenness in resistance value.

  Further, with respect to the mesh-like functional pattern of Example 3 and the mesh-like functional pattern of Comparative Example 2, optical micrographs are shown in FIGS. 9 and 10, respectively. In each photo, the direction from the upper left to the lower right is the first direction (the direction of the first parallel line pattern), and the direction from the lower left to the upper right is the second direction (the direction of the second parallel line pattern) It is. According to the present invention, it is understood that the low visibility is excellent according to the comparison of these photographs. Furthermore, it can be seen that no difference in the length of the conductive path is found between the first direction and the second direction, which can prevent the directional unevenness of the resistance value.

  From the above results, the effectiveness of adjusting the average interval A and the average interval B to satisfy the equation (1) “0.9 ≦ B / A ≦ 1.1” can be understood.

  In the first and second embodiments, “the difference (| C−E |) between the surface energy C in the formation region of the first parallel line pattern and the surface energy E outside the formation region of the first parallel line pattern is , “5 mN / m or less” adjustment, or “the contact angle F of the second linear liquid in the formation region of the first parallel line pattern, and the second contact light outside the formation region of the first parallel line pattern By adjusting the difference between the linear liquid and the contact angle G to 10 ° or less, the average interval A and the average interval B satisfy the equation (1) “0.9 ≦ B / A ≦ 1.1”. did. Here, as an example, an example is shown in which the surface energy and the contact angle are adjusted by the surface treatment of the base material and the setting of the ink composition.

  In Examples 3 to 5, after the formation of the first parallel line pattern, but before applying the second linear liquid, the area including the formation area of the first parallel line pattern is cleaned. Thus, the average interval A and the average interval B satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1”. In Example 3, cleaning by heating, cleaning in Example 4 using electromagnetic waves, and cleaning in Example 5 using a solvent were used.

  In the sixth embodiment, “the liquid application amount per length of the second line-like liquid in the formation area of the first parallel line pattern and the second line-form outside the formation area of the first parallel line pattern” The average interval A and the average interval B were made to satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1” by adjusting “the amount of applied liquid per liquid length to be different”.

  In the seventh embodiment, “the difference (| C−E |) between the surface energy C in the formation region of the first parallel line pattern and the surface energy E outside the formation region of the first parallel line pattern is 5 mN / M or less adjustment, “the contact angle F of the second linear liquid in the formation region of the first parallel line pattern, and the second linear liquid outside the formation region of the first parallel line pattern Adjust the difference with the contact angle G to 10 ° or less ”, or“ surface energy D of a solid surface formed by applying and drying a liquid having the same composition as the first linear liquid, and the first parallel By adjusting the difference (| D−E |) with the surface energy E outside the formation region of the line pattern to 5 mN / m or less, the average interval A and the average interval B can be expressed by Equation (1) “0.9 ≦ B It was made to satisfy /A≦1.1 ”.

  In Example 8, the average distance A is adjusted by adjusting “the contact angle of the solvent having the highest boiling point among the solvents in the second linear liquid outside the formation region of the first parallel line pattern to 6 ° or less”. And the average interval B was made to satisfy Formula (1) “0.9 ≦ B / A ≦ 1.1”.

1: base material 2: first line liquid 3: first parallel line pattern 31, 32: line segment 4: second line liquid 5: second parallel line pattern 51, 52: line segment 6: Pattern 7: Droplet Discharge Device X: Intersection

Claims (12)

The functional material is selectively deposited on the edge in the process of applying a first line-like liquid containing the functional material on a substrate and drying the first line-like liquid to obtain the functional material Form a first parallel line pattern composed of two line segments including
Next, a second line-like liquid containing a functional material is applied on the substrate so as to cross the formation region of the first parallel line pattern, and the second line-like liquid is dried in the process of drying the second line-like liquid. By selectively depositing functional material on the edge to form a second parallel line pattern composed of two segments containing the functional material,
When forming a mesh-like functional pattern in which the first parallel line pattern and the second parallel line pattern intersect,
With respect to the interval between the two lines constituting the second parallel line pattern, an average interval A in the formation area of the first parallel line pattern and an average outside the formation area of the first parallel line pattern The formation method of the mesh-like functional pattern adjusted so that the space | interval B may satisfy following formula (1).
0.9 ≦ B / A ≦ 1.1 (1)   As adjustment for satisfying the equation (1), the difference between the surface energy in the formation region of the first parallel line pattern and the surface energy outside the formation region of the first parallel line pattern is 5 mN / m. The formation method of the mesh-like functional pattern of Claim 1 made into the following.   As adjustment for satisfying the equation (1), the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-like liquid, and outside the formation region of the first parallel line pattern The method for forming a mesh-like functional pattern according to claim 1, wherein the difference between the surface energy and the surface energy is 5 mN / m or less.   As adjustment for satisfying the equation (1), the contact angle of the second line-like liquid in the formation area of the first parallel line pattern, and the second angle outside the formation area of the first parallel line pattern The method for forming a mesh-like functional pattern according to claim 1, wherein the difference between the second contact liquid and the contact angle of the second liquid is 10 ° or less.   As adjustment for satisfying the formula (1), the contact angle of the second linear liquid on the solid surface obtained by applying and drying the functional material contained in the first linear liquid, and the first The method for forming a mesh-like functional pattern according to claim 1, wherein a difference between the contact angle of the second line-like liquid and the contact area of the second line-like liquid outside the formation region of the parallel line pattern is 10 ° or less.   As adjustment for satisfying the equation (1), the contact angle of the solvent having the highest boiling point among the solvents in the second line liquid outside the formation region of the first parallel line pattern is set to 6 ° or less A method of forming a mesh-like functional pattern according to claim 1.   As adjustment for satisfying the equation (1), the amount of liquid application per length of the second line-like liquid in the formation area of the first parallel line pattern, and the formation of the first parallel line pattern The method for forming a mesh-like functional pattern according to claim 1, wherein the liquid application amount per length of the second line-like liquid outside the region is made different.   As the adjustment for satisfying the equation (1), after forming the first parallel line pattern, before applying the second line-like liquid, including within the formation area of the first parallel line pattern The method of forming a mesh-like functional pattern according to claim 1, wherein the region is cleaned.   The mesh-like functional pattern according to claim 8, wherein the cleaning is performed by combining one or more selected from cleaning by heating, cleaning by electromagnetic wave, cleaning by solvent, cleaning by gas, and cleaning by plasma. How it is formed.   The method of forming a mesh-like functional pattern according to any one of claims 1 to 9, wherein the functional material is a conductive material.   A mesh-like functional pattern formed by the method of forming a mesh-like functional pattern according to any one of claims 1 to 10. The functional base material provided with the mesh-like functional pattern of Claim 11.

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