WO2015199201A1 - Method for forming mesh-shaped functional pattern, mesh-shaped functional pattern, and functional substrate - Google Patents

Abstract

The purpose of the present invention is to provide a method for forming a mesh-shaped functional pattern in which low visibility can be improved and variations in resistance can be suppressed, a mesh-shaped functional pattern, and a functional substrate. This purpose is achieved by forming a mesh-shaped functional pattern in which parallel line patterns 3, 5 intersect, by applying liquid lines including a functional material to a substrate and causing the functional material to selectively accumulate at edge parts in a drying process, and forming a parallel line pattern 3 configured from two line segments 31, 32, then applying liquid lines including the functional material so that the liquid lines intersect with the parallel line pattern 3 and causing the functional material to selectively accumulate at edge parts in a drying process, and forming a parallel line pattern 5 configured from two line segments 51, 52, an interval between the two line segments 51, 52 constituting the parallel line pattern being adjusted during formation of the mesh-shaped functional pattern so that the expression 0.9 ≤ B/A ≤ 1.1 is satisfied, where A is the average interval in a formation region of the parallel line pattern 3, and B is the average interval outside the formation region.

Description

Method for forming mesh functional pattern, mesh functional pattern and functional substrate

The present invention relates to a method for 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 for forming a fine line pattern including a functional material. However, since photolithography technology has many material losses and the process becomes complicated, a method for improving these has been studied.

For example, there is a method of forming a fine line pattern by continuously applying droplets containing a functional material to a substrate by an ink jet method or the like. However, in the ordinary ink jet method, the width of the fine line cannot be made equal to or less than the diameter of the ejected droplet, and a fine line pattern having a line width of several μm cannot be formed.

As an approach for forming fine lines by the inkjet method, after applying a repellent to the entire surface in advance, a part of the repellent is hydrophilized with a laser to form a hydrophilic / repellent pattern, and droplets are applied by ink jet there. Then, there is a method of forming a fine line. However, this method has a problem that the process becomes complicated by applying a repellent or forming a repellent pattern with a laser.

On the other hand, a method is known in which a functional material, which is a solid content in a droplet, is deposited on the periphery of the droplet using convection inside the droplet to form a pattern having a finer width than the droplet. (Patent Document 1). According to this method, it is possible to form a thin line having a width of several μm that is equal to or smaller 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 having a fine width of conductive fine particles and connecting a plurality of these rings using this method.

However, these methods have a problem in that the number of intersections of rings increases in order to create a conductive path, and transparency is deteriorated.

On the other hand, the present applicant forms a parallel line pattern by separating the conductive material in the liquid applied in a line shape into edges by the movement of the liquid, and further, a transparent made of the parallel line pattern. Forming a conductive film was invented and reported so far (Patent Document 3).

JP 2005-95787 A WO2011 / 051952 Japanese Patent Application Laid-Open No. 2014-38992

Patent Document 3 describes that when forming a parallel line pattern intersecting in a grid pattern, one-pass printing is used to double the amount of ink applied at the intersection, in this case, the intersection Becomes a ring shape that is thicker than the parallel line portion, and the ring-shaped portion may be periodically visually recognized, and there is room for further improvement in terms of low visibility (that is, a property that is difficult to visually recognize).

Therefore, the applicant further studied, and after applying the first linear liquid in one direction and drying to form the first parallel line pattern, the second in a different direction so as to intersect with this. An attempt was made to form a mesh-like functional pattern in which parallel line patterns in different directions intersect each other by applying a line-shaped liquid and drying to form a second parallel line pattern.

However, the interval between the line segments constituting the second parallel line pattern differs between the inside and outside of the first parallel line pattern forming region, thereby causing the line segments to swell and narrow, resulting in low visibility. A new problem was found that would reduce it.

In particular, when the functional material is a conductive material, the length of the conductive path is increased in the direction along the first parallel line pattern due to the swelling and narrowing generated in the second parallel line pattern. A new problem has also been found that it differs in the direction along the parallel line pattern and causes variations in resistance.

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

Further, other problems of the present invention will become apparent from 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 the first line-shaped liquid containing the functional material on the substrate and drying the first line-shaped liquid. Forming a first parallel line pattern composed of two line segments including:
Next, in the process of applying a second line-shaped liquid containing a functional material on the substrate so as to intersect the formation region of the first parallel line pattern, and drying the second line-shaped liquid. By selectively depositing a functional material on the edge to form a second parallel line pattern composed of two line 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,
About the interval between the two line segments constituting the second parallel line pattern, an average interval A within the formation region of the first parallel line pattern and an average outside the formation region of the first parallel line pattern A method of forming a mesh-like functional pattern that is adjusted so that the interval B satisfies the following formula (1).
0.9 ≦ B / A ≦ 1.1 Formula (1)

2.
As an adjustment to satisfy the formula (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. 2. The method for forming a mesh-like functional pattern according to 1 described below.

3.
As an adjustment to satisfy the formula (1), the surface energy of the solid surface coated with the functional material contained in the first linear liquid and dried, and outside the formation region of the first parallel line pattern 2. The method for forming a mesh-like functional pattern according to 1 above, wherein the difference from the surface energy of the mesh is 5 mN / m or less.

4).
As an adjustment to satisfy the equation (1), the contact angle of the second linear liquid in the first parallel line pattern formation region and the first parallel line pattern formation region outside the first parallel line pattern formation region. 2. The method for forming a mesh-like functional pattern according to 1 above, wherein the difference between the contact angle of the line-shaped liquid of 2 and 10 ° or less.

5.
As an adjustment to satisfy the formula (1), the contact angle of the second linear liquid on the solid surface coated with the functional material contained in the first linear liquid and dried, and the first 2. The method for forming a mesh-like functional pattern according to 1 above, wherein a difference from a contact angle of the second linear liquid outside the parallel line pattern forming region is 10 ° or less.

6).
As an adjustment to satisfy the formula (1), the amount of liquid applied per length of the second linear liquid in the formation region of the first parallel line pattern and the formation of the first parallel line pattern 2. The method for forming a mesh-like functional pattern according to 1 above, wherein a liquid application amount per length of the second linear liquid outside the region is different.

7).
As an adjustment to satisfy the formula (1), after forming the first parallel line pattern and before applying the second line-shaped liquid, the inside of the first parallel line pattern forming region is included. 2. The method for forming a mesh-like functional pattern according to 1 above, wherein the region is washed.

8).
8. The mesh-shaped functional pattern according to 7 above, wherein the cleaning includes cleaning by heating, cleaning with electromagnetic waves, cleaning with a solvent, cleaning with gas, and cleaning with a combination of two or more selected from cleaning with plasma. Forming method.

9.
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.
10. A mesh-like functional pattern formed by the method for forming a mesh-like functional pattern according to any one of 1 to 9 above.

11.
11. A functional substrate provided with the mesh-like functional pattern described in 10 above.

Schematic explanatory diagram conceptually illustrating an example of a 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 further another example of the formation method of a mesh-shaped functional pattern The principal part enlarged view which shows the example of formation of the crossing part X The figure explaining an example of the measuring method of the average space | interval A and the average space | interval B 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. Optical micrograph of functional mesh pattern (Example) Optical micrograph of a functional mesh pattern (reference example)

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

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

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

In FIG. 1, 1 is a substrate, 2 is a line-shaped liquid containing a functional material, and 3 is formed by selectively depositing a functional material on the edge of the line-shaped liquid 2. It is a coating film (hereinafter also referred to as a parallel line pattern). Reference numeral 7 denotes an 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 constituted by, for example, an ink jet head provided in the ink jet recording apparatus.

As shown in FIG. 1A, a liquid containing a functional material is discharged from the droplet discharge device 7 while relatively scanning the droplet discharge device 7 and the substrate 1, and a plurality of liquid droplets sequentially discharged are discharged. The liquid droplets coalesce on the substrate to form a line-like liquid 2 containing a functional material.

Then, as shown in FIG. 1B, when the line-shaped liquid 2 is evaporated and dried, a functional material is selectively deposited on the edge of the line-shaped liquid 2 using a coffee stain phenomenon.

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

That is, the drying of the line-shaped liquid 2 arranged on the substrate 1 is faster at the edge compared to the central portion, and the solid content reaches a saturated concentration as the drying proceeds, and the solid content locally reaches the edge of the line-shaped liquid 2. Precipitation occurs. The edge of the line-shaped liquid 2 is fixed by the deposited solid content, and shrinkage in the width direction of the line-shaped liquid 2 due to subsequent drying is suppressed. By this effect, the liquid of the line-shaped liquid 2 forms a convection from the central portion toward the edge so as to compensate for the liquid lost by evaporation at the edge. Since this convection is caused by immobilization of the contact line of the line-shaped liquid 2 accompanying drying and a difference in evaporation amount between the central part and the edge of the line-shaped liquid 2, the solid content concentration, the contact between the line-shaped liquid 2 and the substrate 1 It varies depending on the angle, the amount of the line-shaped liquid 2, the heating temperature of the substrate 1, the arrangement density of the line-shaped liquid 2, or the environmental factors of temperature, humidity, and atmospheric pressure, and can be controlled by adjusting these. .

As a result, as shown in FIG. 1 (c), a parallel line pattern 3 made of fine lines containing a functional material is formed on the substrate 1. The parallel line pattern 3 formed from one line-shaped liquid 2 is composed of a set of two thin lines 31 and 32.

By applying the parallel line pattern forming method as described above, a mesh-like functional pattern formed by intersecting a plurality of parallel line patterns can be formed.

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

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

The shape of the thin line pattern of the functional material can be set by the device that uses 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 a functional material in a mesh-like functional pattern, it can be preferably applied to a transparent surface electrode for a touch panel or the like. From the viewpoint of configuring a surface electrode or the like, it is very effective to increase the number of conductive paths to be meshed with a plurality of parallel line patterns having different formation directions.

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

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

First, as shown in FIG. 2 (a), a line-like liquid 2 is applied in a mesh form on a substrate 1. That is, the line-shaped liquid 2 is applied so as to intersect at the intersection X.

Next, by drying the line-shaped liquid 2, a mesh pattern by the parallel line pattern 3 can be formed as shown in FIG.

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

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

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

In this example, in the method shown in FIG. 2, as shown in FIG. 3A, the amount of ink at the intersection formed by the line-shaped liquid 2 is set larger than that in the other parts.

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

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

The generation of such a ring-shaped part is advantageous in terms of preventing disconnection of the line segments 31 and 32 and facilitating, for example, ensuring conductivity, but such a ring-shaped part is periodically visible. It has been found that there is a limit in terms of further improving the low visibility.

Further, as a method for preventing the line segments 31 and 32 from being cut off at the intersection X, the following methods may be mentioned.

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

First, as shown in FIG. 4A, the line-shaped liquid 2 is applied in a first direction (left and right direction in the figure).

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

Next, as shown in FIG. 4C, the second direction is different from the first direction (in this example, the direction is perpendicular to the first direction and is the vertical direction in the figure). 2 of the line-shaped liquid 4 is applied. That is, the second line-shaped liquid 4 is applied so as to intersect the formation region of the first parallel line pattern 3.

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

As described above, a mesh-like functional pattern is formed by the first parallel line pattern 3 and the second parallel line pattern 5 having different formation directions.

According to this method, the line segments 31, 32 and the line segments 51, 52 can be prevented from being interrupted at the intersection X where the parallel lines having different directions intersect.

FIG. 5 is an enlarged view of a main part showing an example of forming the intersection X. 5A and 5B are reference examples, and FIG. 5C is a diagram for explaining the present invention.

That is, in the example described using FIG. 4, as shown in FIGS. 5A and 5B, at the intersection X, between the line segments 51 and 52 constituting the second parallel line pattern, Swelling (FIG. 5A) and narrowing (FIG. 5B) occur.

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

In particular, when the functional material is a conductive material, due to such swelling or narrowing, the length of the conductive path extends along the first parallel line pattern 3 (first direction) and the second parallel line. It was found that there was room for further improvement from the viewpoint of preventing variation in resistance due to differences in the direction along the pattern 5 (second direction).

In order to improve these, in the example described with reference to FIG. 4, as shown in FIG. 5C, the interval between the two line segments 51 and 52 constituting the second parallel line pattern 5 is as follows. The average interval A within the formation region of the first parallel line pattern 3 and the average interval B outside the formation region of the first parallel line pattern 3 are adjusted so as to satisfy the following formula (1).

0.9 ≦ B / A ≦ 1.1 Formula (1)

As a result, in the obtained mesh-like functional pattern, disconnection of the line segment can be prevented and low visibility can be improved. In particular, when the functional material is a conductive material, the length of the conductive path is reduced. The first direction and the second direction can be made the same with high accuracy, and the effect that the variation in resistance can be suitably suppressed is obtained.

The formation region of the first parallel line pattern 3 can be said to be a region from one line segment 31 to the other line segment 32 constituting the first parallel line pattern. It can also be said to be an application region of the first line-shaped liquid 2 applied to form the line pattern 3.

Regarding the interval between the line segments 51 and 52 constituting the second parallel line pattern 5, the average interval A within the formation region of the first parallel line pattern 3 and the average outside the formation region of the first parallel line pattern 3. The interval B can be an average value of the intervals measured at a plurality of locations.

A plurality of (n) measurement points set to measure the average interval A may be arranged at equal intervals along the second direction in the formation region of the first parallel line pattern 3. preferable. In addition, a plurality (m places) of measurement points set to measure the average interval B are arranged at equal intervals along the second direction outside the region where the first parallel line pattern 3 is formed. Is preferred.

Specifically, the average interval A and the average interval B are preferably measured as follows.

FIG. 6 is a diagram for explaining an example of a method for 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 constituting the first parallel line pattern with respect to the interval between the line segments 51 and 52 constituting the second parallel line pattern 5. It can be obtained as the average of the distances measured at a total of 7 points A ₁ to A ₇ of 2 points A ₁ and A ₂ and 5 points A ₃ to A ₇ inside the line segments 31 and 32. At this time, these seven measurement points A ₁ to A ₇ are positioned at equal intervals along the formation 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 points A ₁ to A related to the average interval A described above with respect to the interval between the line segments 51 and 52 constituting the second parallel line pattern 5. It can be obtained as an average of intervals measured at a total of five measurement points B ₁ to B ₅ adjacent to A ₇ . At this time, these five measurement points B ₁ to B ₅ are a total of seven measurement points A related to the average interval A described above along the second parallel line pattern forming direction (second direction). it can be positioned in the same regular intervals as the ₁ ~ _{a 7.} A total of seven measurement points A ₁ to A ₇ related to the measurement of the average interval A and a total of five measurement points B ₁ to B ₅ related to the measurement of the average interval B are equidistant from each other along the second direction. Can be positioned.

In the illustrated example, 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. It can also be set adjacent to the upper side in the figure. At this time, measurement points 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, a case has been described in which _two measurement points for the average interval A include two points A ₁ and A ₂ along the line segments 31 and 32 constituting the first parallel line pattern. , 32 may be included along one of them. Further, the portions along the line segments 31 and 32 may not be included.

In the example of FIG. 6, the case where the measurement points for the average interval A include five points A ₃ to A ₇ inside the line segments 31 and 32 constituting the first parallel line pattern has been described. There is no need to be five places, and two or more places are preferable.

In the example of FIG. 6, the case where the measurement points for the average interval B include five points B ₁ to B ₅ outside the line segments 31 and 32 constituting the first parallel line pattern has been described. There is no need to be five places, and two or more places are preferable.

The interval between the line segments 51 and 52 constituting the second parallel line pattern 5 measured at each measurement point in order to obtain the average interval A and the average interval 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 diagram for explaining a cross section taken along line (viii)-(viii) in FIG. 7, and is a cross section obtained by cutting a set of two thin lines included in the pattern in a direction orthogonal to the line segment direction Surface).

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

It can also be said that the adjustment to satisfy the above-described formula (1) is to adjust one or more factors that can affect the ratio B / A of the average interval A and the average interval B. Such factors are not particularly limited and can be appropriately selected.

The following can be illustrated as a preferable aspect of the adjustment for satisfying the above-described formula (1).

In the first aspect, as an adjustment to satisfy the above-described formula (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 are The difference is set to 5 mN / m or less.

Here, the surface energy in the formation region of the first parallel line pattern 3 can be the surface energy measured in the central region between the line segments 31 and 32 constituting the first parallel line pattern. Alternatively, as an alternative method, the surface energy in the formation region of the first parallel line pattern 3 is prepared by separately preparing a base material similar to the base material 1 and the first linear liquid 2 on the base material. The surface energy measured in the central region of the dried film can be obtained after 20 μL of the same liquid is dropped and dried under the same conditions as when the first linear liquid 2 is dried.

On the other hand, the surface energy outside the region where the first parallel line pattern 3 is formed is the surface energy of the substrate 1 in the region where the first linear liquid 2 for forming the first parallel line pattern 3 is not applied. It can be.

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

By setting the difference in surface energy to 5 mN / m or less, it is possible to reduce the change in wettability with respect to the second linear liquid 4 inside and outside the formation region of the first parallel line pattern 3. Formula (1) mentioned above can be satisfy | filled suitably.

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

On the other hand, when the surface energy in the formation region of the first parallel line pattern 3 is smaller than that outside the formation region, if the difference in surface energy exceeds 5 mN / m, the line segment 51 in the second parallel line pattern 5 is obtained. , 52 becomes a cause of narrowing.

The means for adjusting the surface energy difference between the inside and outside of the formation region of the first parallel line pattern 3 is not particularly limited, for example, a method of performing a surface treatment on the region including the outside of the formation region of the first parallel line pattern 3; A method of changing the liquid composition of the first line-like liquid 2 is preferable.

As a method of performing the surface treatment on the region including the outside of the region where the first parallel line pattern 3 is formed, the surface treatment for changing the surface energy with respect to the substrate 1 is performed before forming the first parallel line pattern 3. The method of giving can be mentioned. The surface treatment may be performed only on a region outside the formation region of the first parallel line pattern 3, or may be performed on a region including the outside of the formation region and the inside of the formation region. It is also preferable to perform a surface treatment on the entire surface of the substrate 1.

When changing the liquid composition of the first line-shaped liquid 2, it can be performed by selecting a blending component (functional material, additive, solvent, etc.), adjusting a blending amount of each component, or the like.

In the second aspect, as the adjustment for satisfying the above-described formula (1), the surface energy of the solid surface coated with the functional material contained in the first linear liquid 2 and dried, and the first parallel lines The difference from the surface energy outside the formation region of the pattern 3 is set to 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 linear liquid 2 on an arbitrary substrate, and the surface energy of the substrate itself and It refers to the surface of the solid film coated with the substrate so that the contact angle does not affect the surface energy and the contact angle on the surface of the solid film. Application | coating of a functional material can be performed by apply | coating the coating liquid containing this functional material, for example. A liquid having the same composition as that of the first line-like liquid 2 may be used as the coating liquid for forming the solid surface.

In the region where the first parallel line pattern 3 is formed, the region between the line segments 31 and 32 is in the first line-shaped liquid 2 that 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 non-uniform.

At this time, the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-shaped liquid 2 is an index for realizing more reliable adjustment to satisfy the above-described formula (1). obtain. That is, even if a large amount of residual components are present in the region between the line segments 31 and 32, it is unlikely to affect the interval between the line segments 51 and 52 beyond the effect 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 outside the region where the first parallel line pattern 3 is formed, if the difference in surface energy exceeds 5 mN / m, the second line-like liquid 4 will spread due to wetting and spreading. In the parallel line pattern 5, this 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 outside the region where the first parallel line pattern 3 is formed, if the difference in surface energy exceeds 5 mN / m, the line segment 51 in the second parallel line pattern 5 This causes a narrowing between 52.

The means for adjusting the difference between 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 for the first aspect can be preferably used.

In the third aspect, as an adjustment to satisfy the above-described formula (1), the contact angle of the second linear liquid 4 in the formation region of the first parallel line pattern 3 and the first parallel line pattern 3 The difference from the contact angle of the second linear liquid 4 outside the formation region is set to 10 ° or less.

Here, the contact angle in the formation region of the first parallel line pattern 3 can be a contact angle measured in the central region 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 by separately preparing a base material similar to the base material 1, and the first linear liquid 2 and the base material 1 on the base material. A contact angle measured in the central region of the dried film may be obtained after 20 μL of the same liquid is dropped and dried under the same conditions as those for drying the first linear liquid 2.

On the other hand, the contact angle outside the formation region of the first parallel line pattern 3 is such that the first line-shaped liquid 2 for forming the first parallel line pattern 3 is not applied on the base material 1 in the region. It can be a contact angle.

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

By making the difference in the contact angle 10 ° or less, the change in wettability with respect to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3. In the parallel line pattern 5, the interval between the line segments 51 and 52 can be set to satisfy the above-described expression (1).

When the contact angle in the formation region of the first parallel line pattern is larger than the contact angle outside the formation region, if the difference in contact angle exceeds 10 °, the second linear liquid 4 is wet and spread. In the formation region of one parallel line pattern 3, the interval between the line segments 51 and 52 of the second parallel line pattern 5 becomes larger than outside the formation region, resulting in a bulging shape.

On the other hand, when the contact angle in the formation region of the first parallel line pattern is smaller than the contact angle outside the formation region, if the contact angle difference exceeds 10 °, the contact angle in the formation region of the first parallel line pattern 3 In FIG. 5, the interval between the line segments 51 and 52 of the second parallel line pattern 5 becomes smaller than outside the formation region, resulting in a narrow shape.

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

In the fourth aspect, as an adjustment for satisfying the above-described formula (1), the contact of the second linear liquid 4 on the solid surface coated with the functional material contained in the first linear liquid 2 and dried. The difference between the corner and the contact angle of the second linear liquid 4 outside the region where the first parallel line pattern 3 is formed is set to 10 ° or less. Here, regarding the “solid surface”, the description in the second aspect is incorporated.

By making the difference in the contact angle 10 ° or less, the change in wettability with respect to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3. In the parallel line pattern 5, the interval between the line segments 51 and 52 can be set to satisfy the above-described expression (1).

In the second aspect, as described above for the surface energy, 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 region where the first parallel line pattern 3 is formed, if the difference in contact angle exceeds 10 °, the second linear liquid 4 is wet and spread. In the formation region of one parallel line pattern 3, the interval between the line segments 51 and 52 of the second parallel line pattern 5 becomes larger than outside the formation region, resulting in a bulging shape.

On the other hand, when the contact angle on the solid surface is smaller than the contact angle outside the region where the first parallel line pattern 3 is formed, if the difference in contact angle exceeds 10 °, the region inside the region where the first parallel line pattern 3 is formed In FIG. 5, the interval between the line segments 51 and 52 of the second parallel line pattern 5 becomes smaller than outside the formation region, resulting in a narrow shape.

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

In the fifth aspect, as an adjustment to satisfy the above-described formula (1), 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. Is 6 ° or less.

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

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

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

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

In the sixth aspect, as the adjustment for satisfying the above-described formula (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 liquid application amount per length of the second linear liquid 4 outside the formation area of the parallel line pattern 3 is made different.

For example, when the wettability of the second linear liquid 4 is better in the formation region than outside the formation region of the first parallel line pattern 3, the length per second length of the second linear liquid 4 in the formation region The liquid application amount is relatively small with respect to the outside of the formation region.

Further, for example, when the wettability of the second linear liquid 4 is better outside the formation region than within the formation region of the first parallel line pattern 3, the length of the second linear liquid 4 in the formation region. The per-liquid application amount is relatively increased with respect to the outside of the formation region.

In this way, the interval between the line segments 51 and 52 of the second parallel line pattern 5 in the formation region of the first parallel line pattern 3 is prevented from expanding or narrowing from the outside of the formation region. The

The difference in the liquid application amount inside and outside the formation region of the first parallel line pattern 3 can be adjusted as appropriate so as to satisfy the expression (1). For example, when the inkjet method is used to form the second line-shaped liquid 4, the number of droplets ejected per unit length of the second line-shaped liquid 4 and the droplet volume per droplet are set to the first The difference in the amount of applied liquid can be set by making the difference between the inside and outside of the region where the parallel line pattern 3 is formed.

In the seventh aspect, as an adjustment for satisfying the above-described formula (1), the first parallel line pattern 3 is formed after the first parallel line pattern 3 is formed and before the second linear liquid 4 is applied. The region including the inside of the formation region is cleaned.

As described above, in the region where the first parallel line pattern 3 is formed, the region between the line segments 31 and 32 is the first line shape that has not been transported 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 non-uniform.

It can also be said that cleaning is removal of such residual components. At this time, how much residual components are removed is affected by the cleaning conditions, for example, the setting of the type and intensity of cleaning. By utilizing this relationship, the difference in wettability of the second linear liquid 4 inside and outside the formation region of the first parallel line pattern 3 can be eliminated. In one aspect, the cleaning is performed by removing residual components so that at least the distance between the line segments 51 and 52 constituting the second parallel line pattern 5 can satisfy the above-described formula (1). possible. In this sense, the cleaning can be positioned as an example of adjustment for satisfying the above-described formula (1).

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

In the case where cleaning is performed only in the formation region of the first parallel line pattern, for example, irradiation with electromagnetic waves 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 giving it in the formation region.

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

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

As a method using electromagnetic waves, a method of irradiating an electron beam, a gamma ray, an ultraviolet ray or the like can be used. The electromagnetic wave irradiation conditions are appropriately set in a range in which the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described formula (1).

The solvent used for cleaning with the solvent is not limited as long as it can satisfy the above-described formula (1), but a solvent that has little influence on the parallel line pattern formed by depositing the functional material may be selected. preferable. A solvent suitable for cleaning can be appropriately selected according to the type of functional material. For example, in the case of water-dispersed silver nanoparticles, an alcohol-based solvent is suitable.

The conditions for cleaning with plasma can be appropriately set so that the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described formula (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 similarly described.

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

The set of two thin lines (line segments) 51 and 52 of the parallel line pattern 5 do not necessarily have an island shape completely independent of each other. As shown in the figure, the two line segments 51 and 52 are connected by the thin film portion 50 formed between the line segments 51 and 52 at a height lower than the height of the line segments 51 and 52. It is also preferable that it is 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 each preferably 10 μm or less. If it is 10 micrometers or less, since it will be a level which cannot be visually recognized normally, it is more preferable from a viewpoint of improving transparency. Considering the stability of the line segments 51 and 52, the line widths W1 and W2 of the line segments 51 and 52 are preferably in the range of 2 μm or more and 10 μm or less, respectively.

Note that the widths W1 and W2 of the line segments 51 and 52 are defined as Z being the height of the thinnest portion where the thickness of the functional material is the thinnest between the line segments 51 and 52, and line segments from the Z. When the protruding heights 51 and 52 are defined as 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 in 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 the line segments 51 and 52 from the surface of the base material 1, respectively. Are defined as the widths 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 very thin, the line segments from the surface of the substrate 1 are ensured from the viewpoint of securing a cross-sectional area and reducing resistance. The heights h1 and h2 of 51 and 52 are preferably higher. 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 preferably in the range of 0.01 or more and 1 or less, respectively.

Further, from the viewpoint of further improving the thinning of the parallel line pattern 5, the height Z of the thinnest part where the thickness of the functional material is the thinnest between the line segments 51 and 52, specifically, the thinnest part 50 is the thinnest. The height Z of the thin part 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 achieve a balance between transparency and stability.

Further, in order 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 the same shape (similar cross-sectional area) to the line segment 51 and the line segment 52. Specifically, the heights h1 and h2 of the line segment 51 and the line segment 52 are substantially equal. Are preferably equal. 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 that the line segments 51 and 52 are not coupled 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 of the line segments 51 and 52 in the line segment direction is preferably 5 times or more of the interval I between the line segments 51 and 52, and more preferably 10 times or more. The length L and the interval I can be set corresponding to the formation length and formation width of the line-shaped liquid 4 for forming the parallel line pattern lines 5.

It is also preferable that the line segments 51 and 52 are connected and formed as a continuous body at the formation start point and end point of the line-shaped liquid 4 (start point and end point over a certain length L in the line segment direction).

Further, it is preferable that the line segments 51 and 52 have substantially the same line widths W1 and W2, and the line widths W1 and W2 are sufficiently narrower than the distance between the two lines (interval I).

Furthermore, it is preferable that the line segment 51 and the line segment 52 constituting the parallel line pattern 5 generated from one line-shaped liquid are formed simultaneously.

In the parallel line pattern 5, it is particularly preferable that each of the line segments 51 and 52 satisfies all the following conditions (a) to (d).

(A) When the height of each line segment 51, 52 is h1, h2, and the height of the thinnest part in each line segment is Z, 5 ≦ h1 / Z and 5 ≦ h2 / Z.

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

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

(D) When 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 formed is not particularly limited. For example, glass, plastic (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyethylene, polypropylene, acrylic , Polyester, polyamide, etc.), metals (copper, nickel, aluminum, iron, etc., or alloys), ceramics, and the like. These may be used alone or in a bonded state. . Among these, plastic is preferable, and polyethylene terephthalate, polyolefin such as polyethylene and polypropylene, and the like are preferable. In particular, PET, PEN and the like that are easily bonded are preferably used. The easy adhesion process is a process for improving the adhesion by modifying the surface of the substrate, 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 line liquid is not particularly limited as long as it is a material for imparting a specific function to the base material. Giving a specific function means, for example, that a conductive material is used as a functional material when imparting conductivity to a base material, and when an insulating property is imparted, the insulating material is functional. Use as a material. Preferred examples of the functional material include conductive materials such as conductive fine particles and conductive polymers, insulating materials, semiconductor materials, optical filter materials, dielectric materials, and the like. In particular, as a functional material in using a transparent conductive film, conductive materials such as conductive fine particles and conductive polymers or conductive material precursors can be preferably exemplified. An electroconductive material precursor refers to what can be changed into an electroconductive material by performing an appropriate process.

The conductive fine particles are not particularly limited, but Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga. In particular, fine particles such as In can be exemplified, and among them, use of fine metal particles such as Au, Ag, and Cu is more preferable because a circuit pattern having low electrical resistance and strong corrosion can be formed. 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. Preferable examples of the carbon fine particles include graphite fine particles, carbon nanotubes, fullerenes and the like.

The conductive polymer is not particularly limited, but a π-conjugated conductive polymer can be preferably exemplified.

The π-conjugated conductive polymer is not particularly limited, and polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, polyparaphenylene vinylenes, poly Chain conductive polymers such as paraphenylene sulfides, polyazulenes, polyisothianaphthenes, and polythiazyl can be used. Among these, polythiophenes and polyanilines are preferable in that high conductivity can be obtained. Most preferred is polyethylene dioxythiophene.

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

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. It consists of a structural unit having a group and a structural unit having no anionic group.

This polyanion is a solubilized polymer that solubilizes a π-conjugated conductive polymer in a solvent. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

Further, it may be a polyanion having F (fluorine atom) in the compound. Specific examples include “Nafion” containing a perfluorosulfonic acid group (manufactured by Dupont), “Flemion” (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group.

Among these, a compound having a sulfonic acid is more preferable because the liquid ejection stability is particularly good when the ink jet printing method is used and high conductivity is obtained.

Further, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate 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 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

A commercially available material can be preferably used as the conductive polymer. For example, a conductive polymer (abbreviated as PEDOT / PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is used in H.264. C. It is commercially available from Starck as the “CLEVIOS” series, from Aldrich as “PEDOT-PASS 483095, 560598” and from Nagase Chemtex as the “Denatron” series. Polyaniline is also commercially available from Nissan Chemical Company as the “ORMECON” series.

In addition, a conductive material precursor can also be preferably used as a functional material particularly in the use of a transparent conductive film, and examples thereof include organic metal complexes, inorganic metal salts, and electroless plating catalysts.

As the liquid containing the functional material, water, an organic solvent, or the like can be used alone or in combination.

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

When using a plurality of solvents together, 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 with respect to the base material of the solvent having the highest boiling point is related to the expression of the coffee stain phenomenon.

In addition, the liquid containing the functional material may contain various additives such as a surfactant as long as the effects of the present invention are not impaired.

It is also preferable to adjust the contact angle with the base material to suitably cause the above-described coffee stain phenomenon by using a surfactant. The surfactant is not particularly limited, but a silicon surfactant or the like can be used. Silicone surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid is polyether-modified, such as “KF-351A” and “KF-642” manufactured by Shin-Etsu Chemical Co., Ltd. and “BYK347” manufactured by Big Chemie. “BYK348” and the like are commercially available. The addition amount of the surfactant is preferably 1% by weight or less with respect to the total amount of the liquid containing the functional material.

The method for applying the line liquid on the substrate is not particularly limited as long as the liquid can be applied in a state having fluidity sufficient to cause the coffee stain phenomenon. Can be used. Particularly preferred methods include, for example, a dispenser method and an ink jet method.

The mesh-like functional pattern of the present invention may be a mesh-like functional pattern obtained as described above and further subjected to post-processing. Functionality can be further enhanced by post-processing. The post-processing is not particularly limited, and examples thereof include plating. For example, the reflectance is preferably reduced by plating.

The functional substrate of the present invention has 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 composed of a mesh-like functional pattern.

The imparting of conductivity to the coating film is performed, for example, by using a conductive material as a functional material, or a post-treatment is performed on a coating film formed using a conductive material precursor as a functional material. It can carry out by providing electroconductivity by giving.

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

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

Since the functional base material is excellent in low visibility of the fine lines constituting the coating film, a remarkable effect is exhibited in applications in which a user views an image through the base material.

In particular, the preferred application of the substrate with a transparent conductive film is, for example, a liquid crystal, plasma, organic electroluminescence, field emission, etc., as a transparent electrode for various types of displays, or a touch panel or the like, from the viewpoint of significantly achieving the effects of the present invention. It can be suitably used as a transparent electrode used in a mobile phone, electronic paper, various solar cells, various electroluminescence light control elements, and the like.

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

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

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the examples.

Example 1
1. Preparation of ink Ink 1 having the following composition was prepared.
-Silver nanoparticle aqueous dispersion 1 (silver nanoparticles: 40 wt%): 1.75 wt%
・ Silicon-based surfactant ("BYK-348" manufactured by Big Chemie): 0.01% by weight
・ Pure water: balance

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

3. Measurement of surface energy and contact angle Before forming the mesh-like functional pattern, the surface energy in the formation region of the first parallel line pattern formed with ink 1 and the contact angle of the second linear liquid are as follows. Measurements were performed by an alternative method.

(1) Measurement of surface energy 20 μL of ink 1 was dropped onto the substrate 1 and dried to form ring-shaped fine lines due to the coffee ring phenomenon around the droplets. Thereafter, the contact angle of water, propylene carbonate, and diiodomethane with respect to the central region inside the ring-shaped thin wire was 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 device “DM-501” manufactured by Kyowa Interface Chemical Co., Ltd. (the same device was also used for measuring the contact angle described below). .) The calculated surface energy value was 56 mN / m. This value was defined as the surface energy C in the first parallel line pattern formation region.

(2) Measurement of the contact angle of the second linear liquid a. Measurement of the contact angle of the second line-shaped liquid in the region where the first parallel line pattern is formed 20 μL of ink 1 is dropped on a polyethylene terephthalate (PET) base material with easy adhesion processing that makes the contact angle with respect to ink 1 22 °. And dried to form ring-shaped fine lines due to the coffee ring phenomenon around the droplets. Thereafter, the contact angle of ink 1 (same composition as the second line-shaped liquid) with respect to the central region inside the ring-shaped thin wire was measured. The measured contact angle was 17 °. This value was defined as the contact angle F of the second line-shaped liquid in the formation region of the first parallel line pattern.

I. Measurement of the contact angle of the second linear liquid outside the region where the first parallel line pattern was formed 3 μL of ink 1 was dropped on the surface of the substrate, and the contact angle of the second linear liquid on the surface of the substrate was measured. . The measured contact angle was 20 °. This value was used as the contact angle G of the second linear liquid outside the region where the first parallel line pattern was formed.

4). Formation of pattern Using an XY robot (“SHOTMASTER300” manufactured by Musashi Engineering) equipped with an inkjet head “512LHX” (standard droplet volume 42 pL) manufactured by Konica Minolta, and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) Ink 1 is sequentially discharged onto the substrate 1 as droplets so that the pitch between the nozzle rows is 282 μm and the pitch between the scanning directions is 45 μm, and the droplets continuously applied in the scanning direction on the substrate are united. As a result, a plurality of line-shaped liquids were formed. In addition, in the process of heating the stage on which the substrate is placed while printing at 70 ° C. and drying these line-shaped liquids, the solid content is deposited on the periphery, so that one set of two lines from one line-shaped liquid. The parallel line pattern was formed.

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

In this way, a mesh-like functional pattern in which the first parallel line pattern and the second parallel line pattern intersect at a right angle was formed. The overall size of the mesh-like functional pattern is 50 mm × 50 mm.

(Example 2)
1. Preparation of ink Ink 2 having the following composition was prepared.
-Silver nanoparticle aqueous dispersion 2 (silver nanoparticles: 40 wt%): 1.75 wt%
・ Silicon-based surfactant (BYK-348 manufactured by Big Chemie): 0.01%
・ Pure water: balance

The silver nanoparticle aqueous dispersion 2 is different from the silver nanoparticle aqueous dispersion 1 used in Example 1 in the dispersant.

2. Preparation of substrate The substrate 1 (surface energy E = 52 mN / m) was used as the substrate.

3. Measurement of surface energy and contact angle As a result of measuring in the same manner as in Example 1 by replacing the ink 1 of Example 1 with the 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 line-shaped liquid in the first parallel line pattern formation region is 25 °, and the contact angle G of the second line-shaped liquid outside the first parallel line pattern formation region is 21 °.

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 changed to the ink 2.

Example 3
1. Ink preparation Ink 1 was used as the ink.

2. Preparation of base material As the base material, the base material 2 made of a PET base material having a surface energy of 48 mN / m by easy adhesion processing (surface treatment) was used.

3. Measurement of surface energy and contact angle The substrate 1 of Example 1 was replaced with the substrate 2 and measured in the same manner as in Example 1. As a result, the surface energy C in the formation region of the first parallel line pattern was 56 mN / m. The contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. G was 28 °.

4). Formation of pattern Using an XY robot (“SHOTMASTER300” manufactured by Musashi Engineering) equipped with an inkjet head “512LHX” (standard droplet volume 42 pL) manufactured by Konica Minolta, and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) Ink 1 is sequentially discharged onto the substrate 2 as droplets so that the pitch between the nozzle rows is 282 μm and the pitch between the scanning directions is 45 μm, and the droplets continuously applied in the scanning direction are combined on the substrate. As a result, a plurality of line-shaped liquids were formed. In addition, in the process of heating the stage on which the substrate is placed while printing at 70 ° C. and drying these line-shaped liquids, the solid content is deposited on the periphery, so that one set of two lines from one line-shaped liquid. The parallel line pattern was formed.

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

After cleaning by heating, the substrate is rotated by 90 °, and a plurality of second line-shaped liquids with ink 1 are applied in a direction orthogonal to the first parallel line pattern by the same method as described above, and dried. Thus, a second parallel line pattern was formed.

In this way, a mesh-like functional pattern in which the first parallel line pattern and the second parallel line pattern intersect at a right angle was formed. The overall size of the mesh-like functional pattern is 50 mm × 50 mm.

Example 4
In Example 3, a mesh pattern was formed in the same manner as in Example 3 except that the cleaning by heating was changed to the cleaning by the following electromagnetic wave.

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

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

<Washing with solvent>
The region including the formation region of the first parallel line pattern was cleaned by immersing in 2 propanol for 10 minutes.

(Example 6)
1. Ink preparation Ink 1 was used as the ink.

2. Preparation of substrate The substrate 2 (surface energy E = 48 mN / m) was used as the substrate.

3. Measurement of surface energy and contact angle The substrate 1 of Example 1 was replaced with the substrate 2 and measured in the same manner as in Example 1. As a result, the surface energy C in the formation region of the first parallel line pattern was 56 mN / m. The contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. G was 28 °.

4). Pattern formation Using an XY robot (“SHOTMASTER300” manufactured by Musashi Engineering) equipped with an inkjet head “512LHX” manufactured by Konica Minolta (standard droplet volume 42 pL) and an inkjet control system (“IJCS-1” manufactured by Konica Minolta) Ink 1 is sequentially discharged onto the substrate 2 as droplets so that the pitch between the nozzle rows is 282 μm and the pitch between the scanning directions is 45 μm, and the droplets continuously applied in the scanning direction are combined on the substrate. As a result, a plurality of line-shaped liquids were formed. In addition, in the process of heating the stage on which the substrate is placed while printing at 70 ° C. and drying these line-shaped liquids, the solid content is deposited on the periphery, so that one set of two lines from one line-shaped liquid. The parallel line fine line pattern was formed.

Thereafter, the substrate is rotated by 90 °, a plurality of second line-shaped liquids with ink 1 are applied in a direction orthogonal to the first parallel line pattern, and dried to form the second parallel line pattern. Formed. At this time, when the ink is applied, the liquid application amount per length of the second line-shaped liquid in the first parallel line pattern formation region is set to the liquid application amount outside the first parallel line pattern formation region. The coating was adjusted to 70%.

In this way, a mesh-like functional pattern in which the first parallel line pattern and the second parallel line pattern intersect at a right angle was formed. The overall size of the mesh-like functional pattern is 50 mm × 50 mm.

(Example 7)
1. Ink preparation Ink 1 was used as the ink.

2. Preparation of base material As the base material, the base material 3 made of a PET base material having a surface energy E of 56 mN / m by easy adhesion processing (surface treatment) was used.

3. Measurement of surface energy and contact angle First, an aqueous dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight) is applied to the substrate 3 with a wire bar # 7 and dried to obtain a functional material (silver). A solid surface of (nanoparticles) was prepared. The surface energy of this solid surface was measured and found to be 61 mN / m. This value was defined as the surface energy D of the solid surface obtained by applying and drying a liquid having the same composition as the first linear liquid.

Moreover, the base material 1 of Example 1 was replaced with the base material 3, and as a result of measuring similarly to Example 1, the surface energy C in the formation area of the first parallel line pattern was 56 mN / m. The contact angle F of the second linear liquid in the parallel line pattern formation region 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 substrate 1 was replaced with the substrate 3 in Example 1.

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

2. Preparation of substrate The substrate 1 (surface energy E = 52 mN / m) was used as the substrate.

3. Measurement of contact angle Using a contact angle measuring device “DM-501” manufactured by Kyowa Interface Chemical Co., Ltd., the contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C.) outside the formation region of the first parallel line pattern was measured. The angle H was 5 °. In addition, it was set as the value 5 seconds 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 the ink 1 was replaced with the ink 4 in Example 1.

(Comparative Example 1)
1. Ink preparation Ink 1 was used as the ink.

2. Preparation of substrate The substrate 2 (surface energy E = 48 mN / m) was used as the substrate.

3. Measurement of surface energy and contact angle The substrate 1 of Example 1 was replaced with the substrate 2 and measured in the same manner as in Example 1. As a result, the surface energy C in the formation region of the first parallel line pattern was 56 mN / m. The contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. 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 substrate 1 was replaced with the substrate 2 in Example 1.

(Comparative Example 2)
1. Preparation of ink Ink 3 having the following composition was prepared.
-Silver nanoparticle aqueous dispersion 3 (silver nanoparticles: 40 wt%): 1.75 wt%
・ Silicon-based surfactant ("BYK-348" manufactured by Big Chemie): 0.01% by weight
・ Pure water: balance

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

2. Preparation of substrate The substrate 2 (surface energy E = 48 mN / m) was used as the substrate.

3. Measurement of surface energy and contact angle As a result of measuring in the same manner as in Example 1 with the ink 1 of Example 1 replaced with the ink 3 and the substrate 1 replaced with the substrate 2, the first parallel line pattern formation region The inner surface energy C is 61 mN / m, the contact angle F of the second linear liquid in the first parallel line pattern formation region is 12 °, and the outside of the first parallel line pattern formation region. 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 substrate 1 was replaced with the substrate 2 in Example 1.

(Comparative Example 3)
1. Ink preparation Ink 4 was used as the ink.

2. Preparation of substrate The substrate 2 (surface energy E = 48 mN / m) was used as the substrate.

3. Measurement of contact angle Using a contact angle measuring device “DM-501” manufactured by Kyowa Interface Chemical Co., Ltd., the contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C.) outside the formation region of the first parallel line pattern was measured. The angle H was 8 °. In addition, it was set as the value 5 seconds 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 substrate 1 was replaced with the substrate 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 first parallel line pattern forming region is formed with respect to the interval between two line segments constituting the second parallel line pattern. The average interval A was calculated as the average value of the intervals measured at the _seven measurement points A ₁ to A ₇ described in FIG. Further, with respect to the interval between the two line segments constituting the second parallel line pattern, the average interval B outside the first parallel line pattern forming region is set to a total of five measurement points B ₁ to B described in FIG. It was calculated as the mean value of the measured intervals in B _5. Further, from the values of the average interval A and the average interval B, the value of B / A in the above formula (1) was obtained.

It is possible to determine whether or not the above-described equation (1) is satisfied by obtaining the B / A value. That is, it can also be determined whether or not the adjustment for satisfying the above-described expression (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: A thing like a periodic pattern cannot be visually recognized, but it looks uniform over the whole B: A thing like a periodic pattern can be visually recognized

-Evaluation method for uneven direction of resistance value For the mesh-like functional patterns obtained in Examples 1 to 7 and Comparative Examples 1 and 2, the uneven direction of resistance value was evaluated by the following method.

Cut out a strip of 50 mm in length and 10 mm in width parallel to the direction of the first parallel line pattern (first direction), attach measuring electrodes with silver paste to both ends of the long side (that is, the short side), and between the terminals of the strip The resistance of was measured with a tester. Similarly, the resistance between the terminals is measured with a tester even in a strip having a length of 50 mm and a width of 10 mm in parallel with the direction of the second parallel line pattern (second direction), and the resistance in the first direction and the second direction. The ratio of was evaluated. Specifically, the ratio of the resistance is 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 as a fraction.

As a standard, it is practically preferable that the resistance ratio is 10% or less, and when the resistance ratio exceeds 10%, it can be evaluated that it is not practically preferable.

The 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 were adjusted so as to satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1”, the low visibility was excellent. It can be seen that the uneven direction of the resistance value can be prevented. On the other hand, Comparative Examples 1 to 3 in which such adjustment was not performed are inferior in low visibility, and it is found that uneven resistance value cannot be sufficiently prevented.

Furthermore, optical micrographs are shown in FIGS. 9 and 10 for the mesh-like functional pattern of Example 3 and the mesh-like functional pattern of Comparative Example 2, respectively. In each photograph, 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. From the comparison of these photographs, it can be seen that the present invention is excellent in low visibility. Further, it can be seen that there is no difference in the length of the conductive path between the first direction and the second direction, and thus it is possible to prevent unevenness of the resistance value.

From the above results, the effectiveness of adjusting so that the average interval A and the average interval B satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1” is understood.

In Examples 1 and 2, the difference between the surface energy C in the first parallel line pattern formation region and the surface energy E outside the first parallel line pattern formation region (| CE |) "Adjust to 5 mN / m or less", or "Contact angle F of the second linear liquid in the first parallel line pattern formation region and the second outside the first parallel line pattern formation region" By adjusting the difference from the contact angle G of the line liquid to 10 ° or less, the average interval A and the average interval B satisfy the expression (1) “0.9 ≦ B / A ≦ 1.1”. did. Here, as an example, the example in which the surface energy and the contact angle are adjusted by the surface treatment of the substrate and the setting of the ink composition is shown.

In Examples 3 to 5, “After cleaning the first parallel line pattern and before applying the second line-shaped liquid, the region including the first parallel line pattern forming region is cleaned” adjustment Thus, the average interval A and the average interval B were made to satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1”. In Example 3, cleaning by heating was used, in Example 4, cleaning by electromagnetic waves, and in Example 5, cleaning by solvent was used.

In Example 6, “the amount of liquid applied per length of the second line-shaped liquid in the first parallel line pattern formation region and the second line shape outside the first parallel line pattern formation region” By adjusting “different the amount of liquid applied per length of the liquid”, the average interval A and the average interval B were made to satisfy the formula (1) “0.9 ≦ B / A ≦ 1.1”.

In Example 7, the difference (| CE−) between the surface energy C in the first parallel line pattern formation region and the surface energy E outside the first parallel line pattern formation region is 5 mN. Adjustment to “/ m or less”, “the contact angle F of the second line-shaped liquid in the first parallel line pattern formation region, and the second line-shaped liquid outside the first parallel line pattern formation region” The difference from the contact angle G is adjusted to 10 ° or less, or “the surface energy D of the 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 |) from the surface energy E outside the formation area of the line pattern to 5 mN / m or less ”, the average interval A and the average interval B are expressed by the equation (1)“ 0.9 ≦ B /A≦1.1 ”.

In Example 8, by adjusting “the contact angle of the solvent having the highest boiling point out of the solvent in the second linear liquid outside the first parallel line pattern formation region is 6 ° or less”, the average interval A The average interval B satisfies the formula (1) “0.9 ≦ B / A ≦ 1.1”.

1: Substrate 2: First line-shaped liquid 3: First parallel line pattern 31, 32: Line segment 4: Second line-shaped liquid 5: Second parallel line pattern 51, 52: Line segment 6: Pattern 7: Droplet ejection device X: Intersection

Claims (12)

1. The functional material is selectively deposited on the edge in the process of applying the first line-shaped liquid containing the functional material on the substrate and drying the first line-shaped liquid. Forming a first parallel line pattern composed of two line segments including:
   Next, in the process of applying a second line-shaped liquid containing a functional material on the substrate so as to intersect the formation region of the first parallel line pattern, and drying the second line-shaped liquid. By selectively depositing a functional material on the edge to form a second parallel line pattern composed of two line 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,
   About the interval between the two line segments constituting the second parallel line pattern, an average interval A within the formation region of the first parallel line pattern and an average outside the formation region of the first parallel line pattern A method of forming a mesh-like functional pattern that is adjusted so that the interval B satisfies the following formula (1).
   0.9 ≦ B / A ≦ 1.1 Formula (1)
2. As an adjustment to satisfy the formula (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 method for forming a mesh-like functional pattern according to claim 1 to be described below.
3. As an adjustment to satisfy the formula (1), the surface energy of the solid surface coated with the functional material contained in the first linear liquid and dried, 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 from the surface energy of the mesh is 5 mN / m or less.
4. As an adjustment to satisfy the equation (1), the contact angle of the second linear liquid in the first parallel line pattern formation region and the first parallel line pattern formation region outside the first parallel line pattern formation region. The method for forming a mesh-like functional pattern according to claim 1, wherein the difference between the contact angle of the two line-shaped liquids is 10 ° or less.
5. As an adjustment to satisfy the formula (1), the contact angle of the second linear liquid on the solid surface coated with the functional material contained in the first linear liquid and dried, and the first 2. The method for forming a mesh-like functional pattern according to claim 1, wherein a difference from a contact angle of the second linear liquid outside the parallel line pattern formation region is 10 ° or less.
6. As an adjustment to satisfy the formula (1), 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 is set to 6 ° or less. The method for forming a mesh-like functional pattern according to claim 1.
7. As an adjustment to satisfy the formula (1), the amount of liquid applied per length of the second linear liquid in the formation region of the first parallel line pattern and the formation of the first parallel line pattern The method for forming a mesh-shaped functional pattern according to claim 1, wherein a liquid application amount per length of the second line-shaped liquid outside the region is made different.
8. As an adjustment to satisfy the formula (1), after forming the first parallel line pattern and before applying the second line-shaped liquid, the inside of the first parallel line pattern forming region is included. The method for forming a mesh-like functional pattern according to claim 1, wherein the region is washed.
9. 9. The mesh-shaped functional pattern according to claim 8, wherein the cleaning is performed by cleaning using a combination of one or more selected from cleaning by heating, cleaning by electromagnetic waves, cleaning by a solvent, cleaning by gas, and cleaning by plasma. Forming method.
10. The method for forming a mesh-like functional pattern according to any one of claims 1 to 9, wherein the functional material is a conductive material.
11. A mesh-like functional pattern formed by the method for forming a mesh-like functional pattern according to any one of claims 1 to 10.
12. The functional base material provided with the mesh-shaped functional pattern of Claim 11.
    

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