TWI554338B - Pattern forming method, substrate having transparent conductive film, image display device and electronic equipment for image displaying - Google Patents

Description

Pattern forming method, transparent conductive film substrate, image display device, and electronic device for image display

The present invention relates to a pattern forming method, a transparent conductive film substrate, an apparatus, and an electronic device, and more particularly, to a functional material that is selectively deposited on the edge of a liquid by drying. A pattern forming method for patterning engineering, and a transparent conductive film substrate, device, and electronic device obtained by the method.

As a method of forming a fine line pattern containing a functional material, a method using a photolithography method is widely used in the prior art. However, in the photolithography method, since the loss of materials is large and the engineering system is complicated, the method for improving these problems is reviewed.

For example, there is a method of forming a fine line pattern by continuously applying a droplet containing a functional material to a substrate by an inkjet method or the like. However, in the usual inkjet method, the width of the thin line cannot be obtained. It is assumed that the diameter of the discharged droplets is equal to or smaller than the diameter of the droplets of several μm.

As an attempt to form a fine line by an inkjet method, there is a method in which a liquid-repellent agent is applied to a whole substrate in advance, and a laser is irradiated to partially hydrophilize one of the liquid-repellent agents to form a liquid-repellent portion and a hydrophilic portion. A partially formed pattern, and a method of imparting droplets by ink jetting to form a thin line for the hydrophilic portion. However, in this method, since it is necessary to apply a liquid-repellent and to perform patterning by laser, there is a problem that the engineering is complicated.

On the other hand, it is known that a functional material having a solid amount in a liquid droplet is deposited on the peripheral portion of the liquid droplet by convection inside the liquid droplet, and a fine wide pattern is formed by the liquid droplet. Method (Patent Document 1). According to this method, it is not necessary to carry out special work, and it becomes a thin line which can form a width of several micrometers below the diameter of a droplet.

Further, Patent Document 2 describes a method in which a fine and wide ring of conductive fine particles is formed by this method, and the transparent conductive film is formed by a plurality of connections.

However, in such methods, in order to make a conductive path, the intersection of the rings is increased, and there is a problem that the transparency is lowered.

In view of this, the applicant of the present invention has proposed a technique in which a conductive material imparted to a linear liquid is separated to the edge by the movement of the liquid, and is formed by a pair. The parallel line pattern formed by the thin lines further forms a transparent conductive film formed by the parallel line pattern (Patent Document 3).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-95787

[Patent Document 2] WO2011/051952

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2014-38992

When a transparent conductive film formed by a parallel line pattern is used as, for example, a transparent electrode used in an image display device, it is known that even if the pattern itself is difficult to be visually recognized, transparency is obtained. For the best, when this group is incorporated into the image display device, the ripple (interference pattern) is visually recognized.

In view of this, it is known that the direction in which the parallel line patterns are formed is the same in the direction in which the pattern of the image display device (for example, the pattern of the image array) is formed in the same direction. ripple.

In order to achieve this configuration in detail, it is conceivable to change the cutting direction of the substrate on which the transparent conductive film formed by the parallel line pattern is formed, but in this case, it is easy to cause loss of surface extraction efficiency. .

On the other hand, although it is also conceivable to change the direction in which the parallel line pattern is formed with respect to the substrate, as in Patent Document 3, When it is described that the linear liquid is formed along the moving direction of the inkjet head, it is necessary to change the arrangement angle of the inkjet head with respect to the substrate, and the productivity is improved. There are problems on it.

When the pattern including the parallel line pattern is formed, if the degree of freedom in the pattern forming direction with respect to the substrate can be improved without impairing the productivity, the above-described problem of the corrugation can be appropriately prevented.

Therefore, an object of the present invention is to provide a pattern forming method capable of improving the degree of freedom in the pattern forming direction with respect to a substrate without impairing productivity, and a transparent conductive film obtained by the method. Substrates, devices, and electronic machines.

Further, other problems of the present invention will become more apparent from the following description.

The above problems are solved by the following inventions.

A pattern forming method for discharging a droplet discharge device from a plurality of nozzles of a droplet discharge device on a substrate while containing a functional material while moving relative to a substrate When the liquid droplets are formed on the substrate, at least one set of droplets adjacent to each other that are merged into one object is in a direction orthogonal to the direction of movement and a direction orthogonal to the relative movement direction. Any one of them is arranged at intervals, and the droplets of the droplets and one or both of the intervals are adjusted in such a manner that the droplets are combined into one. By laminating the droplets into a linear liquid formed, the functional material is deposited on the edge of the linear liquid and a pattern containing the functional material is formed.

2. The pattern forming method according to the above 1, wherein, in the formation of the linear liquid, a plurality of nozzles are arranged in parallel with respect to a nozzle row of the droplet discharge device. The set of droplets is provided as a complex array in a direction intersecting the nozzle row, and the droplets of the complex array are combined to form one, and the aforementioned line extending in a direction crossing the nozzle row is formed liquid.

3. The pattern forming method according to the above 1 or 2, wherein the droplet capacity and the droplet capacity are improved by combining the droplets to form a linear portion of the linear liquid formed One or both of the aforementioned intervals are adjusted.

4. The pattern forming method according to any one of the above 1 to 3, wherein a total liquid droplet volume V [pL] is discharged from one of the nozzles for forming one of the linear liquids. And a nozzle column resolution R[npi] in a direction orthogonal to the aforementioned relative movement direction of the plurality of nozzles, and the product V‧R[pL‧npi] of the two is adjusted to 4.32×10 ⁴ [pL‧npi] The range below 5.18 × 10 ⁵ [pL‧npi].

5. The pattern forming method according to any one of the above 1 to 4, wherein the droplet volume is adjusted by adjustment of the gradation.

6. The pattern forming method according to any one of the above 1 to 5, wherein a contact angle of the liquid droplets discharged from the liquid droplet discharging device on the substrate is 10 [°] or more The range below 30 [°].

7. The pattern forming method according to any one of the above 1 to 6, wherein one or a plurality of the linear liquids are formed by one pass of the relative movement.

8. The pattern forming method according to any one of the above 1 to 7, wherein, when the linear liquid which is parallel to each other is formed by one pass of the relative movement, The interval between the linear liquids is adjusted to suppress mutual interference when the adjacent linear liquid is dried.

9. The pattern forming method according to any one of the above 1 to 8, wherein the linear liquid which is parallel to each other is formed by one pass of the relative movement, and the line is The adjustment of the interval between the liquids is adjusted by one or both of the time interval at which the droplets are ejected from the respective nozzles and the relative movement speed of the droplet discharge device relative to the substrate. Come and do it.

The method of forming a pattern according to any one of the above 1 to 9, wherein the linear liquid is formed by a plurality of parallel liquids which are parallel to each other by the relative movement. The interval between the liquids is adjusted to 400 [μm] or more.

11. The pattern forming method according to any one of the above 1 to 10, wherein, in order to promote the combination of the droplets, one of the linear liquids is formed to be formed from each other The maximum discharge time difference Δt _max of the liquid containing the functional material discharged from the adjacent nozzles is adjusted to 200 [ms] or less.

12. The pattern shape as described in any one of the above 1 to 11. In the method of providing the first linear liquid on the substrate, and selectively depositing the functional material on the edge during drying of the first linear liquid, a first parallel line pattern including two line segments of the functional material, and then the second line is provided on the substrate so as to intersect the formation region of the first parallel line pattern Forming a liquid, and selectively depositing the functional material on the edge portion during drying of the second linear liquid to form a second parallel line formed by two line segments including the functional material The line pattern forms a pattern in which the first parallel line pattern and the second parallel line pattern intersect at at least one intersection.

The pattern forming method according to the above 12, wherein the interval between the two line segments constituting the second parallel line pattern is an average interval A between the formation regions of the first parallel line patterns. The average interval B outside the formation region of the first parallel line pattern satisfies the following formula (1), and is adjusted: 0.9 ≦ B / A ≦ 1.1 ‧ ‧ formula (1)

14. The pattern forming method according to the above-mentioned item 13, wherein the surface energy in the formation region of the first parallel line pattern and the formation of the first parallel line pattern are satisfied as the adjustment to satisfy the expression (1) The difference between the surface energies outside the area is set to 5 mN/m or less.

15. The pattern forming method according to the above-mentioned item 13, wherein the coating material for applying the functional material contained in the first linear liquid is applied and dried to satisfy the adjustment of the above formula (1). Between the surface energy and the surface energy outside the formation region of the first parallel line pattern The difference is set to 5 mN/m or less.

16. The pattern forming method according to the above-described item 13, wherein the contact angle of the second linear liquid in the region where the first parallel line pattern is formed is adjusted to satisfy the adjustment of the above formula (1). The difference between the contact angles of the second linear liquid outside the formation region of the first parallel line pattern is 10 or less.

17. The pattern forming method according to the above-mentioned item 13, wherein the adjustment of the formula (1) is performed by applying a functional material contained in the first linear liquid and drying it. The difference between the contact angle of the second linear liquid on the surface and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern is 10 or less.

18. The method of forming a grid-like functional pattern according to the above-described item 13, wherein the adjustment to satisfy the expression (1) is performed by the second portion outside the formation region of the first parallel line pattern. The contact angle of the solvent having the highest boiling point among the solvents in the linear liquid is set to 6 or less.

The method of forming a pattern according to the above-described item 13, wherein the adjustment of the expression (1) is performed per unit length of the second linear liquid in a region where the first parallel line pattern is formed. The liquid application amount and the liquid application amount per unit length of the second linear liquid outside the formation region of the first parallel line pattern are different from each other.

20. The pattern forming method according to the above 13, wherein In order to satisfy the adjustment of the above formula (1), after the first parallel line pattern is formed, the area in the formation region including the first parallel line pattern is washed before the second linear liquid is supplied. net.

The pattern forming method according to the above 20, wherein the washing is performed by washing by heating, washing by electromagnetic waves, washing by a solvent, or gas. Washing of one or a combination of two or more selected from the washing and the washing by the plasma.

The pattern forming method according to any one of the above 1 to 21, wherein, in the drying of the linear liquid, a treatment for promoting drying is applied.

The method of forming a pattern according to any one of the above-mentioned items, wherein the content of the functional material of the liquid discharged from the droplet discharge device is 0.01% by weight or more and 1% by weight or less. range.

The pattern forming method according to any one of the above 1 to 23, wherein the functional material is a conductive material or a conductive material precursor.

A transparent conductive film substrate comprising a transparent conductive film comprising a pattern formed by the pattern forming method according to any one of 1 to 24 above, which is provided on a surface of a substrate. .

An apparatus comprising the transparent conductive film substrate as described in 25 above.

27. An electronic machine characterized in that it is provided as before The device described in 26.

According to the present invention, it is possible to provide a pattern forming method which can improve the degree of freedom in pattern formation direction of a substrate without impairing productivity, and a transparent conductive film substrate and image obtained by the method. Display device and electronic device for image display.

1‧‧‧Substrate

2‧‧‧1st linear liquid

20‧‧‧ droplets

3‧‧‧1st parallel line pattern

31, 32‧‧‧ line segment (thin line)

4‧‧‧2nd linear liquid

5‧‧‧2nd parallel line pattern

51, 52‧‧ ‧ line segment (thin line)

6‧‧‧ pattern

7‧‧‧Drop ejection device

71‧‧‧Inkjet head

72‧‧‧ nozzle

8‧‧‧Drying device

9‧‧‧ bracket

D‧‧‧ Relative movement direction of the droplet discharge device relative to the substrate

E‧‧‧Transport direction of substrate

X‧‧‧Intersection

Fig. 1 is a perspective cross-sectional view conceptually illustrating a pattern in which a parallel line pattern is formed from a linear liquid.

Fig. 2 is a plan view conceptually illustrating one example (comparative example) of a method of forming a linear liquid.

Fig. 3 is a plan view conceptually illustrating an example (comparative example) of a method of forming a grid-like pattern.

Fig. 4 is a plan view conceptually showing a surface of a substrate formed by patterning by the method shown in Fig. 3.

Fig. 5 is a plan view conceptually illustrating another example (comparative example) of a method of forming a grid-like pattern.

Fig. 6 is a plan view conceptually showing a surface of a substrate on which a pattern is formed by the method shown in Fig. 5.

Fig. 7 is a plan view conceptually illustrating an example of a pattern forming method of the present invention.

FIG. 8 is a plan view conceptually illustrating an example of droplet discharge conditions discharged from a droplet discharge device.

Fig. 9 is a plan view conceptually explaining another example of the droplet discharge condition ejected from the droplet discharge device.

FIG. 10 is a plan view conceptually illustrating still another example of the droplet discharge condition discharged from the droplet discharge device.

[Fig. 11] is an enlarged view of a portion shown by (xi) in Fig. 10.

Fig. 12 is a plan view conceptually showing an example of forming a plurality of linear liquids by a plurality of passes.

Fig. 13 is a plan view conceptually showing an example of a case where a grid-like pattern is formed by using the pattern forming method of the present invention.

Fig. 14 is a plan view conceptually illustrating another example in the case of forming a grid-like pattern using the pattern forming method of the present invention.

Fig. 15 is a plan view conceptually illustrating a configuration example of a drying device.

Fig. 16 is a plan view conceptually illustrating another example of the pattern forming method of the present invention.

Fig. 17 is a plan view conceptually illustrating another form of droplets for forming a linear liquid.

Fig. 18 is a plan view conceptually showing a linear liquid formed by the form of Fig. 17;

Fig. 19 is a plan view conceptually illustrating a parallel line pattern formed from the linear liquid shown in Fig. 18.

FIG. 20 is a view for explaining a nozzle row.

Fig. 21 is an explanatory diagram for explaining an example of a method of forming a grid-like functional pattern.

Fig. 22 is an explanatory diagram for explaining another example of a method of forming a grid-like functional pattern.

Fig. 23 is an explanatory diagram for explaining still another example of a method of forming a grid-like functional pattern.

Fig. 24 is an enlarged view showing an important part of the formation of the intersection portion X.

Fig. 25 is an optical micrograph of a functional pattern in the form of a grid.

FIG. 26 is a diagram for explaining an example of a method of measuring the average interval A and the average interval B.

Fig. 27 is a partially enlarged plan view showing an example of a parallel line pattern formed on a substrate.

FIG. 28 is an explanatory view for explaining a cross section taken along line (a)-(a) of FIG. 27.

Fig. 29 is a partially omitted perspective view showing an example of a parallel line pattern formed on a substrate.

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

Figure 1 is a perspective cross-sectional view conceptually illustrating a pattern of parallel line patterns formed from a linear liquid, the section corresponding to the phase The longitudinal section of the cut is made in a direction orthogonal to the direction in which the linear liquid is formed.

In Fig. 1, 1 is a substrate, 2 is a linear liquid containing a functional material, and 3 is a coating formed by selectively depositing a functional material at the edge of the linear liquid 2. Film (hereinafter, also referred to as a parallel line pattern).

In Fig. 1(a), a linear liquid 2 containing a functional material is applied to a substrate 1.

As shown in Fig. 1(b), when the linear liquid 2 containing the functional material is evaporated and dried, the functional material is selectively used at the edge of the linear liquid 2 by the coffee stain phenomenon. Stacked up.

The coffee stain phenomenon can be produced by setting the conditions when the linear liquid 2 is dried.

That is, the drying of the linear liquid 2 disposed on the substrate 1 is faster at the edge than the central portion, and the solid concentration reaches the saturated concentration as the drying progresses, and is linear. At the edge of the liquid 2, local precipitation of solid content occurs. Due to the solid content precipitated therefrom, the edge portion of the linear liquid 2 is in a state of being fixed, and the shrinkage in the width direction of the linear liquid 2 is suppressed accompanying the subsequent drying. The liquid of the linear liquid 2 forms a convection from the central portion toward the edge portion in such a manner as to complement the amount of liquid lost at the edge portion due to evaporation. This convection is caused by the difference in the contact line of the linear liquid 2 accompanying the drying and the difference in the amount of evaporation between the central portion and the edge portion of the linear liquid 2, so that it is adapted to the solid shape. Volume concentration, The contact angle of the linear liquid 2 and the substrate 1, the amount of the linear liquid 2, the heating temperature of the substrate 1, the arrangement density of the linear liquid 2, or the environmental factors of temperature, humidity, and air pressure can be changed by For these adjustments to control.

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

The application of the linear liquid on the substrate can be carried out using a droplet discharge device. Specifically, while the droplet discharge device is relatively moved relative to the substrate, the liquid containing the functional material is discharged from the nozzle of the droplet discharge device, and the discharged droplets are combined on the substrate. In one case, it is possible to form a linear liquid containing a functional material. The droplet discharge device can be constituted, for example, by an inkjet head provided in the inkjet recording device.

Here, the subject matter discovered by the inventors will be described in detail with reference to a comparative example.

Fig. 2 is a plan view conceptually illustrating one example (comparative example) of a method of forming a linear liquid.

In Fig. 2, 7 is a droplet discharge device, and is constituted by an inkjet head 71. 72a to 72f are nozzles provided in the ink jet head 71.

From the viewpoint of imparting a liquid to a line shape, as shown in Fig. 2, a method of forming the linear liquid 2 along the relative movement direction D of the droplet discharge device 7 can be considered.

When the linear liquid material 2 is formed, the droplet discharge device 7 is relatively moved with respect to the substrate 1, and the functional material is continuously discharged from one nozzle 72a of the inkjet head 71. Liquid. By combining the discharged droplets on the substrate 1 to form one, it is possible to form the linear liquid 2 along the relative movement direction of the droplet discharge device 7.

A plurality of linear liquids 2 can be formed by operating the same in the same manner for the other nozzles 72b to 72f.

By causing the linear liquid 2 thus formed to be generally dried as shown in Fig. 1, the parallel line pattern 3 can be formed by the linear liquid 2. The parallel line pattern 3 is formed along the relative moving direction of the droplet discharge device 7. That is, the line segments 31, 32 constituting the parallel line pattern are formed along the relative moving direction of the droplet discharge device 7.

With this method, it is possible to form a grid-like pattern in which parallel line patterns are crossed each other.

Fig. 3 is a plan view conceptually illustrating an example (comparative example) of a method of forming a grid-like pattern.

First, as shown in FIG. 3(a), the droplet discharge device (not shown in FIG. 3) is moved along the relative movement direction D with respect to the substrate 1, and the first direction is formed in the direction D. Linear liquid 2. Here, the relative movement direction D is a direction along the one side of the rectangular base material 1 (the left-right direction on the drawing).

By drying the first linear liquid 2 as described above, it is possible to form each of the first linear liquids 2 as shown in Fig. 3(b). The first parallel line pattern 3 is formed. The first parallel line pattern 3 is composed of line segments 31 and 32.

Then, the droplet discharge device is rotated by 90° with respect to the substrate, and the relative movement direction D with respect to the substrate 1 is rotated by 90° with respect to the direction in which the first linear liquid 2 is formed. . In this way, the relative movement direction D is changed.

Next, as shown in FIG. 3(c), the droplet discharge device is moved along the changed relative movement direction D, and a plurality of second linear liquids 4 are formed in the direction D. Here, the relative movement direction D is a direction (upward and downward direction on the drawing) along the other side orthogonal to the one side of the rectangular base material 1.

By drying the second linear liquid 4 as described above, the second parallel line pattern 5 can be formed by each of the second linear liquids 4 as shown in FIG. 3(d). The second parallel line pattern 5 is composed of line segments 51 and 52.

In this manner, a grid-like pattern 6 in which the first parallel line pattern 3 and the second parallel line pattern 5 are intersected with each other can be formed. The first parallel line pattern 3 is formed in a direction along one side of the rectangular base material 1, and the second parallel line pattern 5 is formed to be orthogonal to the one side In the direction of the other side.

In the pattern forming method shown in Fig. 3, the following problems can be found.

Fig. 4 is a plan view conceptually showing the surface of a substrate formed by patterning by the method shown in Fig. 3.

The substrate 1 on which the pattern 6 is formed is surface-received and used for a predetermined size in cooperation with the device into which it is incorporated. In the figure, the cut-out line when the face is taken is shown by the broken line C.

First, as shown in Fig. 4(a), it is considered that the substrate is cut and used along the side of the substrate 1. In this case, it can be seen that it is possible to perform face extraction of four sheets.

However, in this case, it is known that the pattern 6 itself which is cut along the cut line C (hereinafter, there is a case called "substrate sheet") is not itself It is visually recognized that when the substrate sheet is incorporated into the apparatus, the direction in which the pattern 6 of the substrate sheet is formed and the direction in which the pattern is formed in the apparatus are easily overlapped, and the corrugations are easily visually recognized.

Here, the "forming direction of the pattern 6" is a direction in which the line segments constituting the pattern (for example, the line segments 31, 32, 51, and 52 described above) are formed, and may include a plurality of directions. In the example of Fig. 4(a), the pattern 6 is formed in a direction corresponding to the direction along the side of the substrate sheet.

In addition, as the above-mentioned "pattern of the device", for example, a lattice-like pattern like a pixel array in the image display device can be preferably exemplified.

On the other hand, as shown in FIG. 4(b), the substrate 1 is cut out in a direction inclined with respect to the side of the substrate 1. That is, the cut line C is set to be inclined in the direction with respect to the side of the substrate 1. Here, the tilt angle is set to 45°.

In the cut substrate piece, the direction in which the pattern 6 is formed is inclined from the direction along the side of the substrate sheet. Thereby, it is possible to prevent the corrugation when the substrate sheet is incorporated into the apparatus.

However, since the direction in which the substrate sheet is cut out is not along the side of the substrate 1, the efficiency of surface pick-up is easily lost. For example, in the case of the substrate 1 having the same area, in the example of Fig. 4(a), four faces can be taken. In contrast, in the example of Fig. 4(b), the limit system is used. It is only possible to take two faces.

Therefore, in the pattern forming method shown in Fig. 3, it has been found that there is a problem in that it is desired to simultaneously achieve the prevention of corrugation and the efficiency of surface pick-up.

Further, in the pattern forming method shown in FIG. 3, when the first linear liquid is supplied and when the second linear liquid is supplied, it is necessary to change the relative movement direction D of the liquid droplet discharging device with respect to the substrate. . For example, it is necessary to change the arrangement direction of the substrate or to change the arrangement direction of the droplet discharge device, and it has been found that there is a problem from the viewpoint of productivity.

Fig. 5 is a plan view conceptually illustrating another example (comparative example) of a method of forming a grid-like pattern.

In the example of FIG. 5, from the viewpoint of preventing the corrugation, the relative movement direction D of the droplet discharge device (not shown in FIG. 5) is set to a direction inclined with respect to the side of the substrate 1.

First, as shown in FIG. 5(a), the droplets are spit in a relative movement direction D inclined at 45° with respect to the side of the substrate 1. The device moves and a plurality of first linear liquids 2 are formed in the direction D.

By drying the first linear liquid 2, as shown in FIG. 5(b), the first parallel line pattern 3 can be formed by each of the first linear liquids 2. The first parallel line pattern 3 is composed of line segments 31 and 32.

Then, the droplet discharge device is rotated by 90° with respect to the substrate, and the relative movement direction D with respect to the substrate 1 is rotated by 90° with respect to the direction in which the first linear liquid 2 is formed. . In this way, the relative movement direction D is changed.

Next, as shown in FIG. 5(c), the droplet discharge device is moved along the relative movement direction D which is inclined with respect to the side of the substrate 1, and a plural number is formed in the direction D. The second linear liquid 4.

By drying the second linear liquid 4 as described above, the second parallel line pattern 5 can be formed by each of the second linear liquids 4 as shown in FIG. 5(d). The second parallel line pattern 5 is composed of line segments 51 and 52.

In this manner, a grid-like pattern 6 in which the first parallel line pattern 3 and the second parallel line pattern 5 are intersected with each other can be formed. The first parallel line pattern 3 and the second parallel line pattern 5 are formed in a direction inclined with respect to the side of the rectangular base material 1.

Fig. 6 is a plan view conceptually illustrating a surface on which a patterned substrate is formed by the method shown in Fig. 5. versus 4 is the same, in the figure, the cut-out line when the face is taken is shown by the broken line C.

As shown in FIG. 6, even if the substrate 1 is cut out along the side of the substrate 1 in order to improve the surface extraction efficiency, since the pattern 6 is formed on the side opposite to the substrate 1 In the direction in which it is inclined, it is possible to prevent the corrugation.

In this way, by forming the pattern 6 in a direction inclined with respect to the side of the substrate 1, it is possible to simultaneously achieve the prevention of the corrugation and the improvement of the efficiency of the surface pick-up.

However, in the pattern forming method shown in FIG. 5, similarly to the method shown in FIG. 3, when the first linear liquid 2 is supplied and when the second linear liquid 4 is supplied, it is necessary to make the relative The relative movement direction D of the droplet discharge device of the substrate is changed. Therefore, in terms of improving productivity, it is found that there is still room for further improvement.

Hereinafter, the pattern forming method of the present invention will be described in detail.

Fig. 7 is a plan view conceptually illustrating an example of the pattern forming method of the present invention.

In Fig. 7, 7 is a droplet discharge device, and is constituted by an inkjet head 71. 72a to 72f are nozzles provided in the ink jet head 71.

While the droplet discharge device 7 is relatively moved relative to the substrate 1, the liquid from the liquid containing the functional material is discharged from the substrate 1 from the plurality of nozzles 72a to 72f of the droplet discharge device 7. drop. The droplets ejected from the mutually different nozzles are combined into one on the substrate 1 On the other hand, the linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D. In the example shown in the figure, the case where one linear liquid 2 is formed by one pass by relative movement is shown, but it is once passed by relative movement. It is also desirable to form a plurality of linear liquids 2.

In the following description, the angle (inclination angle) θ with respect to the direction in which the linear liquid 2 is formed in the relative movement direction D means an angle of clockwise rotation (right rotation) from the relative movement direction D. In the following description, when the angle is a negative value, it can be converted to the angle of the positive value of the counterclockwise rotation (left rotation). In the illustrated example, the inclination angle θ is 45°.

Next, the combination of the droplets on the substrate 1 described above will be described in detail.

Fig. 8 is a plan view conceptually illustrating an example of a droplet discharge condition from a droplet discharge device.

In the illustrated example, 2a to 2f represent the hit positions of the liquid droplets discharged from the nozzles 72a to 72f of the ink jet head 71 provided in the liquid droplet discharging device 7, respectively.

The hit positions 2a to 2f are arranged regardless of whether they are in the relative movement direction D and the direction orthogonal to the relative movement direction D. In other words, the discharge of the liquid droplets from the nozzles 72a to 72f of the ink jet head 71 provided in the liquid droplet discharging device 7 is adjacent to each other on the substrate 1 The droplet, whether in the relative movement direction D and in the relative movement direction D The direction of the exchange is vacant and configured. Here, the term "interval" means the distance between the centers of the droplets. Further, the "drops adjacent to each other" are at least one set of droplets adjacent to each other, and are spaced apart in any of the relative movement direction D and the direction orthogonal to the relative movement direction D. can. In addition, "whether or not the direction of the relative movement and the direction perpendicular to the relative movement direction are arranged at intervals", the reference is arranged to be relative to the relative movement direction. Tilting direction.

In the illustrated example, during the movement of the droplet discharge device 7, the nozzles 72a from the one end side toward the nozzle end 72f on the other end side are arranged in the order from the respective nozzles 72a, 72b, 72c, 72d. At 72e and 72f, droplets are discharged with a time difference to form the above-described arrangement state.

Hit the droplets at the positions 2a to 2f of the above, and then, in order to merge the adjacent droplets on the substrate 1 into one, the droplet volume and the liquid for the droplets One or both of the intervals of the drops are adjusted.

As a result of such an adjustment, the linear liquid 2 can be formed in a direction inclined with respect to the relative movement direction D of the liquid droplet ejection device 7 with respect to the substrate 1. By drying the linear liquid 2, a functional material can be deposited on the edge of the linear liquid 2, and a pattern containing the functional material can be formed, for example, the parallel line pattern described above can be formed. The direction in which the pattern is formed may be a direction that is inclined with respect to the relative movement direction D.

According to the invention, for example, in the form of a linear liquid In the case of the orientation, since it is not necessary to change the arrangement angle of the droplet discharge device, the following effects can be obtained: that is, the relative performance can be obtained without impairing productivity. The degree of freedom in the pattern forming direction of the substrate is increased.

Further, in the case where the above-described liquid droplets are combined into one, and the linearity of the edge portion of the formed linear liquid 2 is further increased, the liquid for the liquid droplets is further improved. It is also desirable to adjust one or both of the drop capacity and the interval of the droplets. Thereby, the linearity of the pattern containing the functional material at the edge of the linear liquid 2 to be deposited can be improved.

As an ideal adjustment example, a total liquid droplet volume V[pL] and a nozzle column resolution R[npi] which are provided from one nozzle for forming one linear liquid 2 are preferable. The product V‧R[pL‧npi] of the two is adjusted to a range of 4.32 × 10 ⁴ [pL‧npi] or more and 5.18 × 10 ⁵ [pL‧npi] or less.

Here, the total droplet volume V[pL] given from one nozzle for forming one linear liquid 2 means a linear liquid for forming one from each of the nozzles 72a to 72f. The total droplet capacity assigned to each of the 2 hit positions 2a to 2f. Therefore, the total droplet capacity, for example, when a plurality of droplets are hit from one nozzle 72a for one hit position 2a, refers to the total capacity of the plurality of droplets. When one droplet is hit from one nozzle 72a for one hit position 2a, it means the capacity of one droplet.

As a method of adjusting the total amount of droplets, a method of adjusting the unit capacity of one droplet or a method of adjusting the number of droplets at a hit position of one hit is preferably exemplified. . It is also desirable to use one or more of these methods in combination.

When the number of droplets at a hit position hitting one is adjusted, a droplet discharge device having a gradation changing means can be suitably used. That is, the droplet capacity can be adjusted by adjusting the gradation. The gradation refers to the number of droplets hit for each point (the unit uses "dpd" (drops per dot), and can be used as a droplet at a hit position hitting one of the above. The number corresponds to the value to use.

Therefore the total volume of the droplet V [pL], the volume of the droplet when a droplet of each set V _d [pL], and the case where the gradation is set to N [dpd] When, based can be expressed as V =V _d ‧N.

Further, the nozzle row resolution R[npi] refers to the number of nozzles per one turn in a direction orthogonal to the relative moving direction. If the nozzle spacing (the distance between the centers of the nozzles (also referred to as the pitch)) in the direction orthogonal to the relative movement direction is constant, the reciprocal of the nozzle spacing [inch] can be used as the nozzle column. The resolution R[npi] corresponds to the value used.

When the product V‧R[pL‧npi] is in the range of 4.32 × 10 ⁴ [pL‧npi] or more and 5.18 × 10 ⁵ [pL‧npi] or less, it is easy to form a linear liquid more linearly. It is possible to appropriately prevent the occurrence of bulge. As a result, the line segments constituting the parallel line pattern formed are more easily formed linearly, and the occurrence of disconnection can be appropriately prevented. Therefore, when a conductive material is used as the functional material, the following effects can be obtained: that is, the sheet resistance and the terminal resistance of the obtained pattern can be further improved.

Preferably, the droplets containing the functional material discharged from the droplet discharge device have a contact angle on the substrate of 10 [°] or more and 30 [°] or less.

In addition, the contact angle is a static contact angle. For example, the droplet to be measured can be measured at 25 ° C and 50% RH by using DM-500 manufactured by Kyowa Interface Science Co., Ltd. (5 μl) was taken from the syringe to the substrate 1, and the angle between the tangent of the end of the droplet and the surface of the substrate was measured and taken out.

The contact angle can be suitably adjusted, for example, by setting the composition of the droplets containing the functional material or the surface energy of the substrate.

When the contact angle is in the range of 10 [°] or more and 30 [°] or less, the following effects can be obtained: that is, the transparency of the formed parallel line pattern can be further improved.

In addition, when the contact angle is in the range of 10 [°] or more and 30 [°] or less, the linear liquid system is more easily formed linearly, and the occurrence of bulge can be appropriately prevented. As a result, the line segments constituting the parallel line pattern formed are more easily formed linearly, and It is also possible to appropriately prevent the occurrence of disconnection and the like. Therefore, when a conductive material is used as the functional material, the following effects can be obtained: that is, the sheet resistance and the terminal resistance of the obtained pattern can be further improved.

In Fig. 8, each of the nozzles 72a to 72f can be formed to form another linear liquid adjacent thereto after the discharge for forming the linear liquid 2 is performed at a specific interval. 2' spit out. In the figure, 2a' to 2f' represent the hit positions of the liquid droplets discharged from the nozzles 72a to 72f in order to form the linear liquid 2'. In this manner, the droplet discharge device 7 can form a plurality of linear liquids at a certain interval in the passage of the relative movement.

In one aspect of the present invention, the linear liquid is formed obliquely with respect to the relative movement direction D of the droplet discharge device and the substrate, and is parallel to each other by the passage of one pass. The interval M _{p of the} linear liquid is easily adjusted to a desired value.

That is, in the case where the linear liquid is generally formed along the relative movement direction D of the droplet discharge device and the substrate as in the comparative example described with reference to FIG. 2, only one time can be used. The adjustment is made in the unit of the nozzle interval of the droplet discharge device by the application interval M _p of the linear liquid to be applied. At this time, the interval M _p that can be selected is a stepwise (discontinuous) value in the unit of the nozzle interval.

On the other hand, the linear liquid is formed obliquely with respect to the relative movement direction D of the droplet discharge device and the substrate, and the adjustment of the application interval M _p is not restricted by the nozzle interval. In other words, it is possible to freely select the interval M _p from the range of continuity.

The interval M _p of the linear liquid to be imparted by one pass is a distance orthogonal to the direction in which the linear liquids 2, 2' are formed as shown in Fig. 8 (also It is called the pitch) and corresponds to the distance between the centers of the linear liquids 2 and 2' in the width direction.

By forming the linear liquid obliquely with respect to the relative movement direction D of the droplet discharge device and the substrate, the interval M _{p is} given, and the time interval at which the droplets can be ejected from the respective nozzles 72a to 72f is provided. And the relative movement speed of the droplet discharge device 7 with respect to the substrate 1, one or both of which are adjusted, and are suitable for adjustment.

For example, with the respective nozzles 72a ~ 72f from the liquid droplet ejection time difference narrow, spaced line is capable of imparting shrink M _p. Further, by increasing the time difference, it is possible to increase the giving interval M _p .

Further, for example, by the base with respect to the droplet ejection apparatus 1 7 relative movement speed is reduced, the line is capable of imparting narrow interval M _p. By increasing the relative moving speed, it is possible to increase the giving interval M _p .

In this way, it is possible to easily adjust the application interval M _p to a desired value. As a result, the degree of freedom in patterning can be improved, and the suitability for various devices or various electronic devices can be improved.

If the interval given by M _{p is} adjusted to the linear for liquid in the adjacent mutual interference when dry 2,2 'for inhibition, is also desirable. Examples of the mutual interference include, for example, interference caused by steam, interference caused by a decrease in temperature of the substrate caused by the loss of heat of vaporization, and the like. By suppressing such mutual interference, it is possible to stabilize the accumulation of the functional material at the edge of the linear liquid, and it is possible to obtain an effect of further improving the bulging prevention property and the transparency. Further, if the functional material is a conductive material, an effect of further improving the sheet resistance and the terminal resistance of the obtained pattern can be obtained.

The value of the interval M _p is not particularly limited, but is preferably 400 [μm] or more. Thereby, it is possible to appropriately suppress the mutual interference when the adjacent linear liquids 2, 2' are dried.

In order to form one linear liquid 2, the maximum discharge time difference Δt _max of the liquid containing the functional material discharged from the adjacent nozzles is preferably 200 [ms] or less. Thereby, the combination of the droplets is promoted to one, and an effect of making the formation of the parallel line pattern more stable can be obtained. In particular, when a conductive material is used as the functional material, an effect of appropriately improving the terminal resistance of the obtained pattern can be obtained.

The maximum discharge time difference Δt _max will be described in detail with reference to the example of Fig. 8 .

In FIG. 8, the droplet discharge device 7 is constituted by one inkjet head 71. At the ink jet head 71, the nozzles 72a to 72f are tied to The droplet discharge device 7 is arranged in a line in the direction in which the relative movement directions are orthogonal to each other.

The droplet discharge device moves toward the relative movement direction D while ejecting the liquid from the nozzle 72a toward the hit position 2a. Next, the droplet discharge device is further moved in the relative movement direction D, and the liquid is discharged from the nozzle 72b adjacent to the nozzle 72a toward the hit position 2b. Therefore, the nozzles 72a and 72b adjacent to each other have a time difference (diffusion time difference) at the timing of discharging the liquid.

In the illustrated example, the nozzles 72a to 72f are arranged in a direction orthogonal to the relative movement direction of the droplet discharge device 7, and are arranged on a straight line, and the discharge time difference between the nozzles adjacent to each other is Any two groups of adjacent nozzles are extracted and will be the same. Under such conditions, the discharge time difference can be set to the maximum discharge time difference Δt _max .

The maximum discharge time difference Δt _{max is} exemplified by other examples.

Fig. 9 is a plan view conceptually explaining another example of the discharge discharge condition of the liquid discharged from the droplet discharge device.

In FIG. 9, the droplet discharge device 7 is constituted by two inkjet heads 71 (hereinafter, referred to as a two-row head).

The two ink jet heads 71 are offset by a distance corresponding to a half of the nozzle interval of each of the ink jet heads 71 in the direction orthogonal to the relative movement direction D. In this manner, by setting the two heads, the nozzle resolution R as the entire droplet discharge device 7 is increased. It is also possible to arrange the heads in more than three columns, and further analyze the nozzles. Degree R increases.

Further, in the figure, at the ink jet head 71 on the right side, the nozzles 72a, 72c, and 72e are not arranged on the straight line in the direction orthogonal to the relative movement direction D. In the figure, the nozzles 72b, 72d, and 72f of the ink jet head 71 on the left side are also the same.

Under such conditions, the difference in the discharge time of the nozzles adjacent to each other differs depending on the extraction method of the adjacent nozzles of the two groups. Under such conditions, the difference in discharge time when two sets of adjacent nozzles are extracted so that the discharge time difference is maximized can be set as the maximum discharge time difference Δt _max .

FIG. 10 and FIG. 11 are plan views for conceptually explaining still another example of the discharge conditions of the liquid droplets discharged from the droplet discharge device. Figure 11 is an enlarged view of a portion shown by (xi) in Figure 10.

When the width of the pattern forming region on the substrate 1 in the direction orthogonal to the relative moving direction D is wider than the width of the ink jet head 71, as shown in the figure, The plurality of ink jet heads 71 can be used in a zigzag manner in a direction orthogonal to the relative moving direction D. In the illustrated example, the two rows of heads formed by the two inkjet heads 71 are arranged in a zigzag shape in a direction orthogonal to the relative movement direction D.

Under such conditions, similarly, the difference in the discharge time of the nozzles adjacent to each other differs depending on the extraction method of the adjacent nozzles of the two groups. In particular, the effect caused by the nozzles adjacent to each other being present at the different heads of the two columns is large. Under the same conditions, the discharge time difference when two sets of adjacent nozzles are extracted so that the discharge time difference is maximized can be set as the maximum discharge time difference Δt _max .

In the example shown in the figure, when the nozzle 72f at the end of the right two rows of heads and the nozzle 72g at the end of the left two rows of heads are taken as the adjacent nozzles, the discharge time difference is maximized. Therefore, this can be set to the maximum discharge time difference Δt _max .

Fig. 12 is a plan view conceptually illustrating an example of forming a plurality of linear liquids by a plurality of passes.

In the illustrated example, an example in which a plurality of linear liquids 2A and 2B are formed by two passes is shown. In the first pass, the linear liquid 2A is formed, and in the second pass, the linear liquid 2B in the same direction as the linear liquid 2A is formed.

It is preferable to provide a drying process for drying the linear liquid formed in the previous passage and forming a parallel line pattern between the respective passes. Here, a drying process is provided between the first pass and the second pass, in which the linear liquid 2A formed in the first pass is dried and parallel lines are formed. Pattern 3.

In this manner, when a linear liquid is formed in a certain passage, it is preferable to dry the linear liquid formed in the previous passage in advance. In this case, it is common for the case where the linear liquid in the same direction is formed in each of the passages as shown in the figure, or the linear liquid in the dissimilar direction is formed in each of the passages.

Followed by a linear imparted by imparting liquids interval _P M, it is desirable, but greater than the line interval M final imparting linear conferred liquid. The linear liquid to be finally applied refers to the linear liquid in the same direction which is imparted by all the passages (in the illustrated example, two passes) for forming the linear liquid in the same direction. . As shown in the figure, when measuring the interval of the linear liquid to be finally applied, some or all of the linear liquid may be in a dry state, that is, it may be parallel. The state of the line pattern. The object in which the linear liquid is dried may be included in the measurement target to which the interval M is applied as the linear liquid to be finally supplied.

As is generally the case, it is preferred that the linear liquid of the same forming direction is intentionally formed by a plurality of passes. In the case where the linear liquid of the same forming direction is formed by a plurality of passes, it is preferable that the second and subsequent passes are in the vicinity of the two adjacent ones given by the previous pass. A new linear liquid is imparted to the gap between the linear liquid (which may also be a dry one). By providing a drying process between the respective passes, it is possible to reduce the amount of the linear liquid which is simultaneously dried, and further to easily ensure the interval between the linear liquids, so that the drying can be caused by the drying. The effect is alleviated, and an effect of making the formation of the parallel line pattern more stable is obtained.

In the example shown in the figure, an example in which a plurality of linear liquids are formed by two passes is shown. However, in the case of passing three or more times, the above description may be applied.

When a linear liquid having the same forming direction is formed by n times (n is an integer of 2 or more), it is preferable to provide the interval M _p by the linear liquid to be applied once. The body is n times the interval M of the linear liquid to be finally imparted.

In the present invention, by forming the linear liquid obliquely with respect to the relative movement direction D of the droplet discharge device and the substrate, the elongation rate of the linear liquid can be made larger than that of the droplet discharge device relative to the substrate. Relatively moving speed is greater.

The elongation rate of the linear liquid is the length per unit time in which the linear liquid is elongated in the direction in which the linear liquid is formed. The elongation velocity of the linear liquid V _L [μm/s], when the relative movement speed of the droplet discharge device relative to the substrate is V _H [μm/s], and the linear liquid is opposed to the substrate When the inclination angle is set to θ [°], it can be expressed as V _L =V _H /|cos θ θ|.

The absolute value of cos θ can be set to 1 or less by forming the linear liquid in a direction inclined with respect to the relative movement direction of the liquid droplet ejection device with respect to the substrate. Thereby, the elongation velocity V _L of the linear liquid can be made larger than the relative movement speed V _{H of the} droplet discharge device with respect to the substrate, that is, it can satisfy V _L > V _H .

As a result, the formation of the linear liquid is accelerated, and the droplets which are the objects to be combined are dried in the unit of droplets, and the combination of the droplets can be promoted to one.

According to the pattern forming method of the present invention described above, it is possible to appropriately solve the above-mentioned problem of desired prevention of both the prevention of corrugation and the efficiency of surface extraction, and the problem of productivity. That is, It is possible to obtain the effect of simultaneously achieving the prevention of the corrugation and the efficiency of the surface pick-up as well as the effect of improving the productivity. In response to this, specific examples will be described below.

Fig. 13 is a plan view conceptually showing an example of a case where a grid-like pattern is formed by using the pattern forming method of the present invention.

First, as shown in FIG. 13(a), the droplet discharge with respect to the substrate 1 is set so as to follow the direction of one side of the rectangular substrate 1 (the horizontal direction on the drawing). The relative movement direction D of the device (not shown in Fig. 13). The droplet discharge device is moved in the relative movement direction D, and a plurality of first linear liquids 2 are formed at specific intervals in a direction inclined with respect to the direction D. Here, the inclination angle θ is set to 45°.

By drying the first linear liquid 2 as described above, the first parallel line pattern 3 can be formed by each of the first linear liquids 2 as shown in FIG. 13(b). The first parallel line pattern 3 is composed of line segments 31 and 32.

Next, the droplet ejection device is moved along the relative movement direction D as shown in FIG. 13(c) without changing the relative movement direction D at the time of formation of the first linear liquid 2, and A plurality of second linear liquids 4 are formed at specific intervals in a direction inclined with respect to the direction D. Here, the inclination angle θ is set to -45°.

By drying the second linear liquid 4 as shown in the figure Generally, as shown in FIG. 13(d), the second parallel line pattern 5 can be formed by each of the second linear liquids 4. The second parallel line pattern 5 is composed of line segments 51 and 52.

In this manner, a grid-like pattern 6 in which the first parallel line pattern 3 and the second parallel line pattern 5 are intersected with each other can be formed.

The first parallel line pattern 3 and the second parallel line pattern 5 are formed in a direction inclined with respect to the side of the rectangular base material 1.

Therefore, even if the substrate 1 is cut out along the side of the substrate 1 in order to improve the surface extraction efficiency, the pattern 6 is formed in a direction inclined with respect to the side of the substrate 1. Therefore, it is possible to prevent the corrugation. Therefore, it is possible to simultaneously achieve the prevention of corrugation and the efficiency of face extraction.

Further, the linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D of the liquid droplet discharging device 7 for the substrate 1, and when the first linear liquid 2 is supplied and the second liquid is supplied In the case of the linear liquid 4, since it is not necessary to change the relative movement direction D of the droplet discharge device with respect to the substrate, productivity can be improved. Since it is not necessary to change the direction with respect to the head of the substrate, it is also possible to prevent complication of the device and complexity of control.

Fig. 14 is a plan view conceptually illustrating another example in the case of forming a grid-like pattern using the pattern forming method of the present invention. In FIG. 14, the configuration shown by the same reference numerals as in FIG. 13 can be referred to in FIG.

First, the first linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D (Fig. 14 (a)). Here, the inclination angle θ is set to 45°.

Next, the first linear liquid 2 is dried to form the first parallel line pattern 3 (FIG. 14(b)).

Next, the relative movement direction D is set to be opposite to the relative movement direction D at the time of formation of the first linear liquid 2 .

In this state, the second linear liquid 4 is formed in a direction inclined with respect to the relative movement direction D (FIG. 14(c)). Here, the inclination angle θ is set to -45°.

Next, the second linear liquid 4 is dried to form the second parallel line pattern 5 (FIG. 14(d)).

In this manner, a grid-like pattern 6 in which the first parallel line pattern 3 and the second parallel line pattern 5 are intersected with each other can be formed.

As described above, the linear liquid is formed in a direction inclined with respect to the relative movement direction D of the liquid droplet discharge device for the substrate, and when the first linear liquid 2 is supplied and the second line is provided In the case of the liquid 4, the relative movement direction D of the droplet discharge device with respect to the substrate can be set to the opposite direction.

Thereby, when the droplet discharge device is moved back and forth once on the substrate 1, the first linear liquid and the second linear liquid can be formed in the forward path and the return path, respectively.

At the droplet discharge device, as described above, generally set to the direction opposite to the relative movement direction D and discharge the droplets, as opposed to It is easy to carry out the teaching, and it is not necessary to carry out the process of resetting the arrangement angle of the droplet discharge device of the substrate, and the like.

In the case of drying the linear liquid, it is preferred to apply a treatment for promoting drying. Thereby, an effect of making the formation of the parallel line pattern more stable can be obtained.

As the treatment for promoting drying, for example, treatment such as heating, air blowing, and irradiation with an energy ray may be exemplified, and one or a combination of two or more may be used.

Preferably, a drying device (also referred to as a dryer) that promotes drying of the linear liquid is used. The drying device may be configured to be capable of performing the above-described drying process. For example, a heater, a blower, an energy ray irradiation device, or the like may be exemplified, and one or a combination of two or more may be used. It.

Fig. 15 is a plan view conceptually illustrating a configuration example of a drying device.

The drying device 8 is preferably provided in such a manner as to move relative to the substrate together with the droplet discharge device 7. It is also preferable to mount the drying device 8 together with the droplet discharge device 7 in the tray 9 used for moving the droplet discharge device 7 as shown in the figure.

In the configuration example of the figure, it is assumed that when the droplet discharge device 7 is reciprocated, the linear liquid is formed only at the forward path, and therefore, the liquid droplet discharge device 7 is disposed behind the relative movement direction D. There is a drying device 8. However, when a linear liquid is formed at both the forward path and the return path, the drying device 8 may be provided at both sides in the moving direction of the liquid droplet discharging device 7.

Further, the drying device may be provided at the side of the substrate. For example, it is also preferable to provide a drying device such as a heater on a platform on which a substrate is placed. Further, it is also preferable to provide a drying device on the side of the droplet discharge device and the substrate side.

In the above description, an example in which the droplet discharge device is relatively moved with respect to the substrate is mainly shown in the case where the substrate is fixed and the droplet discharge device is moved. The present invention is not limited to this example, and may be configured to move the substrate and fix the droplet discharge device.

Further, in order to achieve relative movement, the substrate may be moved and the droplet discharge device may be moved. However, this may cause complicated control. From the viewpoint of making control easy, it is preferable to fix one of the substrate and the droplet discharge device and move the other.

Hereinafter, an example of a case where the substrate is moved and the droplet discharge device is fixed will be described.

Fig. 16 is a plan view conceptually illustrating another example of the pattern forming method of the present invention.

In this example, as the droplet discharge device 7, a line head in which a plurality of ink jet heads are arranged in parallel in a wide direction is used. The line head is covered by the width of the pattern forming area at the substrate. A nozzle is formed on the web.

In this example, two droplet discharge devices 7 made of a line head are used.

The droplet discharge device 7 is fixed, and the elongated substrate 1 is conveyed in such a manner as to be sequentially supplied to the droplet discharge devices 7. The base material 1 is conveyed in a specific direction by a conveying means (not shown). The transport means is not particularly limited, and may be constituted by, for example, a belt conveyor device or the like. In the figure, the conveying direction of the substrate 1 is shown by an arrow E. At this time, the relative movement direction D of the droplet discharge device 7 with respect to the base material 1 is opposite to the conveyance direction E of the base material 1.

Each of the droplet discharge devices 7 is provided with a drying device 8 on the downstream side in the transport direction E of the substrate 1. The substrate 1 is transported in the order of the droplet discharge device 7 on the upstream side, the drying device 8 on the upstream side, the droplet discharge device 7 on the downstream side, and the drying device 8 on the downstream side.

First, the substrate 1 to be conveyed is supplied to the droplet discharge device 7 on the upstream side. Here, the first linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D of the droplet discharge device 7. The inclination angle θ of the first linear liquid 2 is set to 45°.

Next, the region in which the first linear liquid 2 is formed is supplied to the drying device 8 on the upstream side. Here, the first parallel line pattern 3 is formed by drying the first linear liquid 2.

Next, the region in which the parallel line pattern 3 is formed is supplied to the droplet discharge device 7 on the downstream side. Here, the second linear liquid 4 is formed in a direction inclined with respect to the relative movement direction D of the droplet discharge device 7. The inclination angle θ of the second linear liquid 4 is set to -45°.

Next, the region in which the second linear liquid 4 is formed is supplied to the downstream drying device 8. Here, the second parallel line pattern 5 is formed by drying the second linear liquid 4.

In this manner, by forming the linear liquid in a direction inclined with respect to the relative moving direction D of the liquid droplet discharging device for the substrate, it is also suitable to be suitable for moving the substrate and A method of forming a pattern under the condition that the droplet discharge device is fixed (for example, using a pattern forming method having the above-described general line head).

In the above description, when a linear liquid is formed by using a droplet discharge device, the droplets which are supplied from one nozzle for one pixel are plural in the direction intersecting the nozzle row. Although the above-described liquid droplets are combined and formed into a single linear liquid which extends in the direction intersecting the nozzle row, the present invention is not limited thereto. For example, when a linear liquid is formed by using a droplet discharge device, a group of droplets given from a plurality of nozzles in a group of pixels arranged in parallel with respect to a nozzle row of the droplet discharge device is used. It is also preferable to form a complex array in the direction in which the nozzle rows intersect, and to combine the droplets of the complex array to form a linear liquid extending in a direction intersecting the nozzle row. For this form, Refer to Figure 17 to Figure 19 for illustration.

As shown in Fig. 17, in general, the linear liquid 2 is formed obliquely with respect to the relative movement direction D of the droplet discharge device 7.

In other words, the liquid droplet discharging device 7 is relatively moved with respect to the substrate 1, and the droplets 20 containing the functional material are discharged from the liquid droplet discharging device 7 on the substrate 1. The relative movement direction D is set in a direction orthogonal to the direction N of the nozzle row 73 formed by the nozzles 72a to 72j.

In the course of the relative movement, the pixel groups formed by the plurality of pixels (a1, b1, c1) arranged in parallel with respect to the direction N of the nozzle row 73, and the plurality of nozzles 72a, 72b Each of 72c provides a droplet 20, that is, a droplet group.

Next, after the droplet discharge device 7 is relatively moved by one pixel in the relative movement direction α, a plurality of pixels (b2) arranged in parallel with respect to the direction N of the nozzle row 73 are provided. And c2, d2) are formed into one lower pixel group, and the liquid droplets 20 are given from each of the plurality of nozzles 72b, 72c, and 72d, that is, the next liquid droplet group is given. By repeating this, the droplet group is given a complex array in a direction inclined with respect to the direction N of the nozzle row 73.

That is, in the illustrated example, when the pixel group to be targeted by the liquid droplets 20 is selected, a specific pixel is formed in the direction N of the nozzle row with respect to each pixel constituting the previously selected pixel group. The number of offsets (in the example shown in the figure, is one pixel) The next pixel group is selected among the pixels of the next line.

By merging the droplets 20 constituting the plural droplet group into one another, as shown in FIG. 18, it is possible to form a direction which is inclined in the direction N with respect to the nozzle row 73, That is, the linear liquid 2 extends in a direction inclined with respect to the relative movement direction D of the droplet discharge device 7.

Further, when the linear liquid 2 is dried, a functional material is deposited on the edge of the linear liquid 2, and as shown in Fig. 19, a parallel line pattern 3 containing the functional material can be formed. The parallel line pattern 3 formed of one linear liquid 2 is composed of one set of two line segments (thin lines) 31 and 32. The parallel line pattern 3 is formed obliquely along the relative movement direction D of the droplet discharge device 7.

As described above, in the case where the linear liquid 2 is formed obliquely with respect to the relative movement direction D of the droplet discharge device 7, it is performed by a plurality of pixels arranged in parallel with respect to the nozzle row 73. By forming a pixel group and giving a droplet group from a plurality of nozzles, the formation of the linear liquid 2 can be freely increased in width. Further, even when the arrangement interval I of the thin wires 31 and 32 generated by the linear liquid 2 is increased, the occurrence of bulging can be appropriately prevented. In other words, the degree of freedom in setting the arrangement interval I of the thin wires 31 and 32 can be improved without making the formation of the thin wires 31 and 32 containing the functional material unstable.

In the above description, although the case where the number of pixels constituting the pixel group is set to 3 pixels is shown, it is not limited. In this case, it is possible to appropriately set the thin lines 31 and 32 so as to have a desired arrangement interval I. Therefore, it is possible to obtain an effect that the degree of freedom in setting the arrangement interval I can be increased. The number of pixels constituting the pixel group is preferably set to be in the range of 2 pixels to 20 pixels, and more preferably set in the range of 2 pixels to 10 pixels.

In the example of FIGS. 17 to 19, the case where the linear liquid 2 for forming the parallel line pattern 3 is formed is described with respect to the form in which the pixel group is used, but the description can also be applied to In the case where the linear liquid 4 for forming the parallel line pattern 5 crossing the parallel line pattern 3 is formed.

In the above description, the droplet discharge device has been described as being provided with a plurality of nozzles arranged in a line, but the present invention is not limited thereto. For example, as shown in FIG. 20, the droplet discharge device 7 may be a nozzle having a plurality of nozzles arranged in a plurality of columns. In this case, the direction of the nozzle row 73 corresponds to the overall arrangement direction N of the plurality of nozzles.

Next, an adjustment for improving the linearity of the thin lines in the pattern (the grid-like functional pattern) formed by intersecting the parallel line patterns with each other will be described.

It is advantageous to provide a functional pattern in a grid shape in order to realize distribution of a functional material on a substrate while maintaining low visibility.

In particular, the line segments constituting the parallel line pattern formed as described above are capable of realizing a line width of several μm, thereby From the fine line width, the grid-like functional pattern, even if the functional material itself is not transparent, it will not be recognized by the human eye, but it looks like transparency.

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

The functional pattern of the mesh shape can be suitably applied to a transparent surface electrode or the like of a touch panel or the like if a conductive material is used as the functional material. From the viewpoint of constituting the surface electrode and the like, it is very effective to form a mesh shape by forming a plurality of parallel line patterns whose directions are different from each other, and it is effective in increasing the conductive path.

As a method of forming such a grid-like functional pattern, the method shown in Fig. 21 can be cited.

First, as shown in Fig. 21 (a), the linear liquid 2 is applied to the substrate 1 in a grid shape. That is, the linear liquid 2 is applied in such a manner as to intersect each other at the intersection X.

Next, by drying the linear liquid 2, as shown in Fig. 21 (b), a grid-like pattern formed by the parallel line patterns 3 can be formed.

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

As a truncation to prevent the line segments 31, 32 at the intersection X The method shown in Fig. 22 can be exemplified.

In this example, in the method illustrated in Fig. 21, as shown in Fig. 22(a), the ink amount of the portion of the intersection formed by the linear liquid 2 is set to be larger than the other portions. And bigger.

According to this method, as shown in Fig. 22 (b), in the grid pattern formed by the parallel line pattern 3, the cutoff of the line segments 31, 32 at the intersection portion X can be prevented.

At this time, since the amount of ink for the intersection portion X is increased, as shown in FIG. 22(b), the intersection portion X is formed to have a larger diameter than the interval between the line segments 31 and 32. ring.

The generation of such a ring portion is advantageous in that, for example, it is advantageous to prevent the line segments 31 and 32 from being cut off, for example, it is easy to ensure conductivity, and the like, but the ring shape is periodically visually recognized. In some cases, it can be seen that there is a limit to the point of further improvement for low visual recognition.

Further, as a method of preventing the cutting of the line segments 31, 32 at the intersection portion X, the method shown in Fig. 23 can also be cited.

First, as shown in Fig. 23 (a), the linear liquid 2 is applied in the first direction (the horizontal direction in the drawing).

In the process of drying the linear liquid 2, the functional material is selectively deposited at the edge portion, and as shown in Fig. 23(b), the first parallel line pattern 3 is formed.

Next, as shown in FIG. 23(c), in the second direction different from the first direction (in this example, it is orthogonal to the first direction) The second linear liquid 4 is applied in the direction, that is, in the upper and lower directions in the figure. In other words, the second linear liquid 4 is applied so as to intersect each other with respect to the formation region of the first parallel line pattern 3.

In the process of drying the linear liquid 4, the functional material is selectively deposited at the edge, and as shown in Fig. 23(d), a second parallel line pattern 5. 51, 52 is formed. It is a line segment constituting the second parallel line pattern 5.

As described above, a grid-like functional pattern formed by the first parallel line pattern 3 and the second parallel line pattern 5 which are formed in mutually different directions is formed.

According to this method, it is possible to prevent the line segments 31, 32 and the line segments 51, 52 from being cut off at the intersection X where the mutually parallel parallel lines intersect.

Fig. 24 is an enlarged view of an important part showing an example of the formation of the intersection portion X.

In the example described using FIG. 23, as shown in FIGS. 24(a) and 24(b), at the intersection X, between the line segments 51, 52 constituting the second parallel line pattern, There is expansion (Fig. 24(a)) and narrowing (Fig. 24(b)). In Fig. 25(a), an optical microscope photograph showing a functional pattern having an expanded mesh shape is shown.

It is known that the expansion or narrowing between the segments 51, 52 is a cause of limitation for the improvement of low visibility.

Also, the department learned: especially when functional materials are In the case of a conductive material, the length of the conductive path is in the direction along the first parallel line pattern 3 (first direction) and the direction along the second parallel line pattern 5 (in the case of the expansion or narrowing) In the 2 directions), there is a difference. From the viewpoint of preventing the variation of the resistance, there is still room for further improvement.

In order to improve on these problems, in the example explained using FIG. 23, as shown in FIG. 24(c), the interval between the line segments 51, 52 constituting the two second parallel line patterns 5 is shown. The adjustment is performed such that the average interval A in 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 satisfy the following formula (1).

0.9≦B/A≦1.1...(1)

Thereby, in the obtained grid-like functional pattern, it is possible to prevent the line segment from being broken, and it is possible to improve the low visibility, especially in the case where the functional material is a conductive material. It is possible to make the length of the conductive path the same in the first direction and the second direction with high accuracy, and it is possible to obtain an effect that the variation of the electric resistance can be appropriately suppressed. In Fig. 25(b), an optical micrograph of a grid-like functional pattern obtained by performing the above general adjustment is shown.

The formation region of the first parallel line pattern 3 means from the line segment 31 constituting one of the first parallel line patterns to the other one. The region up to the square line segment 32 may represent an application region of the first linear liquid 2 to be formed in order to form the first parallel line pattern 3 from another viewpoint.

The interval between the line segments 51 and 52 constituting the second parallel line pattern 5, the average interval A in the region where the first parallel line pattern 3 is formed, and the average interval B outside the region where the first parallel line pattern 3 is formed, The average of the intervals of the measurements made at the plurality of locations can be set separately.

In order to measure the measurement sites of the plurality of places (n places) set by the average interval A, it is preferable to arrange them at equal intervals along the second direction in the formation region of the first parallel line pattern 3. Further, in order to measure the measurement sites of the plurality of places (m places) set by the average interval B, it is preferable to arrange them at equal intervals along the second direction outside the formation region of the first parallel line pattern 3.

The average interval A and the average interval B are preferable, and are generally measured as follows.

Fig. 26 is a view showing an example of a method of measuring the average interval A and the average interval B.

First, the average interval A is as shown in Fig. 26, and is the interval between the line segments 51, 52 constituting the second parallel line pattern 5 as 2 along the line segments 31, 32 constituting the first parallel line pattern. The average of the intervals measured at the seven places A1 to A7 of the five places A3 to A7 at the inner side of the places A1 and A2 and the line sections 31 and 32 is obtained. At this time, the measurement sites of the total of these seven places A1 to A7 are arranged at equal intervals along the forming direction (second direction) of the second parallel line pattern.

On the other hand, the average interval B is as shown in Fig. 26, and is the interval between the line segments 51, 52 constituting the second parallel line pattern 5, and is 7 places in total in relation to the above-mentioned average interval A. The average of the intervals measured at the measurement sites B1 to B5 of the total of five sites adjacent to each other from A1 to A7 is obtained. In this case, the measurement sites B1 to B5 of the total of the five places can be in a total of seven places in the direction in which the second parallel line pattern is formed (the second direction) and the average interval A is the same. The measurement sites A1 to A7 are arranged at equal intervals. The measurement sites A1 to A7 of the total of seven locations that are connected to the measurement of the average interval A, and the measurement sites B1 to B5 of the total of five sites that are connected to the measurement of the average interval B are capable of being mutually aligned along the second direction. Interval for configuration.

In the example shown in the figure, the measurement sites B1 to B5 of the average interval B are displayed adjacent to the lower side in the drawing with respect to the measurement sites A1 to A7 of the average interval A. It can also be set adjacent to the upper side in the figure. In this case, it is preferable to set the average at one of the upper side (one side) and the lower side (the other side) in such a manner that the difference between the average interval A and the average interval B becomes larger. Measurement site B1 to B5 of interval B.

In the example of FIG. 26, the measurement site for measuring the average interval A is described with respect to the two places A1 and A2 including the line segments 31 and 32 constituting the first parallel line pattern, but ,system It may be configured to include one location along one of the line segments 31 and 32. Further, it may be configured not to include a place along the line segments 31, 32.

In the example of FIG. 26, the measurement site for measuring the average interval A is described with respect to the five places A3 to A7 including the line segments 31 and 32 constituting the first parallel line pattern. However, it is not absolutely necessary to have five places, and it is preferable that it is a plurality of places of two or more.

In the example of FIG. 26, the measurement site for measuring the average interval B is described with respect to the five places B1 to B5 including the line segments 31 and 32 constituting the first parallel line pattern. However, it is not absolutely necessary to have five places, and it is preferable that it is a plurality of places of two or more.

The interval between the line segments 51 and 52 of the second parallel line pattern 5 measured at each measurement site in order to extract the average interval A and the average interval B can be defined as follows.

Fig. 27 is a partially enlarged plan view showing an example of a parallel line pattern formed on a substrate. Fig. 28 is an explanatory view for explaining a cross section taken along line (a)-(a) of Fig. 27, and is orthogonal to a group of two thin lines to be included in the pattern with respect to the direction of the line segment. The cut section (longitudinal section) is illustrated in the direction.

The interval I between the line segments 51, 52 constituting the second parallel line pattern 5, as shown in Fig. 28, can be defined as the distance between the largest projections of the line segments 51, 52. Therefore, by each of the above measurement sites The interval I is measured, and the average interval A and the average interval B can be obtained separately.

In order to satisfy the adjustment performed by the above formula (1), it can be said that one or a plurality of factors affecting the ratio B/A of the average interval A and the average interval B are adjusted. Such a factor is not particularly limited and may be suitably selected.

As an ideal form for satisfying the adjustment of the above formula (1), the following aspects are exemplified.

In the first aspect, the adjustment between 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 is satisfied as the adjustment to satisfy the above formula (1). The difference is set to 5 mN/m or less.

Here, the surface energy in the region where the first parallel line pattern 3 is formed can be regarded as the surface energy measured at 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 may be regarded as a substrate prepared separately from the substrate 1, and 20 μL of the first line may be dropped on the substrate. The liquid 2 is the same liquid, and is dried under the same conditions as when the first linear liquid 2 is dried, and then the surface energy measured at the central region of the dried film.

On the other hand, the surface energy outside the formation region of the first parallel line pattern 3 can be regarded as the substrate 1 at a region where the first linear liquid 2 for forming the first parallel line pattern 3 is not provided. Surface energy.

The surface energy can be calculated according to the Young-Fowkes formula.

By setting the difference in the surface energy to 5 mN/m or less, it is possible to reduce the change in the wettability with respect to the second linear liquid 4 inside and outside the region where the first parallel line pattern 3 is formed, and it is possible to appropriately The above formula (1) is satisfied.

When the surface energy in the formation region of the first parallel line pattern 3 is larger than the formation region, if the difference in surface energy exceeds 5 mN/m, the wet diffusion of the second linear liquid 4 is caused. At the second parallel line pattern 5, it causes a cause of expansion between the line segments 51, 52.

On the other hand, when the surface energy in the region where the first parallel line pattern 3 is formed is smaller than the outside of the formation region, if the difference in surface energy exceeds 5 mN/m, at the second parallel line pattern 5, It will become the cause of the narrowing between the segments 51, 52.

The means for adjusting the surface energy difference between the inside and the outside of the formation region of the first parallel line pattern 3 is not particularly limited, but is, for example, a surface for a region other than the formation region including the first parallel line pattern 3. The method of the treatment, the method of changing the liquid composition of the first linear liquid 2, and the like are preferable.

As a method of surface-treating a region including the formation region of the first parallel line pattern 3, a surface treatment for changing the surface energy to the substrate 1 before the formation of the first parallel line pattern 3 is exemplified. The method. The surface treatment may be performed only for a region outside the formation region of the first parallel line pattern 3, or may be performed for a region including the formation region and the formation region. It is also desirable if the surface of the substrate 1 is completely surface treated.

When the liquid composition of the first linear liquid 2 is changed, it can be carried out by selecting a component (a functional material, an additive, a solvent, etc.) or adjusting the amount of each component.

In the second aspect, as the adjustment to satisfy the above formula (1), the surface energy of the flat surface to be coated and dried by applying the functional material contained in the first linear liquid 2 and the first parallel line are used. The difference between the surface energies outside the formation region of the pattern 3 is set to 5 mN/m or less.

The term "flat-coated surface" refers to a surface of a flat coating film which is applied onto a substrate and coated with a functional material contained in the first linear liquid 2, and is dried so that the substrate itself The surface energy and the contact angle of the substrate are coated on the surface of the flat coating film without affecting the surface energy and the contact angle at the surface of the flat coating film. The coating of the functional material can be carried out, for example, by coating a coating liquid containing the functional material. As the coating liquid at the time of forming the flat coating surface, a liquid having the same composition as that of the first linear liquid 2 can also be used.

At a region between the line segments 31, 32 in the formation region of the first parallel line pattern 3, there is a slight residual which is caused by the Coffee Stain phenomenon and is not transported to the line segments 31, 32. The case of some of the components of the first linear liquid 2 at the position. Such a residual component may cause the interval between the line segments 51 and 52 constituting the second parallel line pattern 5 to be uneven.

In this case, the surface energy of the flat surface after the functional material contained in the first linear liquid 2 is applied and dried can be adjusted to satisfy the above formula (1). index. also That is, even if there is a large amount of residual components in the area between the line segments 31 and 32, it is difficult to cause a situation that affects the interval between the line segments 51 and 52 beyond the influence of the flat coated surface. Therefore, by adjusting the difference between the surface energy of the flat coated surface and the surface energy outside the formation region of the first parallel line pattern 3, the reliability can be further improved.

When the surface energy of the flat coating surface is larger than the formation region of the first parallel line pattern 3, if the difference in surface energy exceeds 5 mN/m, the wettability of the second linear liquid 4 is caused by diffusion. At the second parallel line pattern 5, it causes a cause of expansion between the line segments 51, 52.

On the other hand, when the surface energy of the flat coating surface is smaller than the formation region of the first parallel line pattern 3, if the difference in surface energy exceeds 5 mN/m, at the second parallel line pattern 5, It will become the cause of the narrowing between the segments 51, 52.

The means for adjusting the surface energy of the flat surface and the surface energy difference outside the formation region of the first parallel line pattern 3 is not particularly limited, and the means described in connection with the first aspect can be suitably used.

In the third embodiment, the contact angle between the second linear liquid 4 in the region where the first parallel line pattern 3 is formed and the first parallel line pattern 3 are adjusted to satisfy the above formula (1). The difference between the contact angles of the second linear liquid 4 outside the formation region is set to 10 or less.

Here, the contact angle in the region where the first parallel line pattern 3 is formed can be regarded as the contact angle measured at 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 may be regarded as another The same substrate as the substrate 1 was prepared, and 20 μL of the same liquid as the first linear liquid 2 was dropped onto the substrate, and dried under the same conditions as when the first linear liquid 2 was dried. Then, the contact angle measured at the central region of the dried film.

On the other hand, the contact angle outside the formation region of the first parallel line pattern 3 can be regarded as the substrate 1 at the region where the first linear liquid 2 for forming the first parallel line pattern 3 is not provided. Contact angle.

The measurement of the contact angle can be carried out using a contact angle measuring device DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. In the third embodiment, the contact angle is a value obtained after dropping the liquid having the same composition as that of the second linear liquid 4 and then elapsed for 5 seconds.

By setting the difference in the contact angle to 10° or less, it is possible to reduce the change in the wettability of the second linear liquid 4 between the inside and the outside of the region in which the first parallel line pattern 3 is formed. At the parallel line pattern 5, the interval between the line segments 51, 52 satisfies the above formula (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 wet diffusion of the second linear liquid 4 is caused. In the region where the first parallel line pattern 3 is formed, the interval between the line segments 51, 52 of the second parallel line pattern 5 becomes larger than the outside of the formation region, and becomes an expanded 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 difference in contact angle exceeds 10°, the first parallel line pattern 3 is Formation area Inside, the interval between the line segments 51, 52 of the second parallel line pattern 5 becomes smaller than the outside of the formation region, and becomes a narrowed shape.

The means for adjusting the difference in the contact angle is not particularly limited, and the means for adjusting the surface energy in the first embodiment can be suitably used. Further, as a means for adjusting the difference in contact angle, the liquid composition of the second linear liquid 4 can be changed. When the liquid composition of the second linear liquid 4 is changed, it can be carried out by selecting a component (a functional material, an additive, a solvent, etc.) or adjusting the amount of each component. It is also preferable that the liquid of the second linear liquid 4 and the liquid of the first linear liquid 2 are different from each other.

In the fourth aspect, as the adjustment to satisfy the above formula (1), the second line at the flat coating surface after the functional material contained in the first linear liquid 2 is applied and dried is applied. The difference between the contact angle of the liquid 4 and the contact angle of the second linear liquid 4 outside the formation region of the first parallel line pattern 3 is 10 or less. Here, the description of the "flat-coated surface" is made in the second embodiment.

By setting the difference in the contact angle to 10° or less, it is possible to reduce the change in the wettability of the second linear liquid 4 between the inside and the outside of the region in which the first parallel line pattern 3 is formed. At the parallel line pattern 5, the interval between the line segments 51, 52 satisfies the above formula (1).

In the second embodiment, the surface energy is described above. Generally, the adjustment is performed by using the contact angle at the flat surface as an index, and the reliability can be further improved.

When the contact angle at the flat coating surface is larger than the contact angle outside the formation region of the first parallel line pattern 3, if the difference in contact angle exceeds 10°, the second linear liquid 4 is caused. In the wet diffusion, the interval between the line segments 51, 52 of the second parallel line pattern 5 becomes larger outside the formation region and becomes an expanded shape in the region where the first parallel line pattern 3 is formed.

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

The means for adjusting the difference between the contact angle at the flat coating surface and the contact angle outside the formation region of the first parallel line pattern 3 is not particularly limited, and may be appropriately used in connection with the third form. The means of explanation.

In the fifth embodiment, the contact of the solvent having the highest boiling point among the solvents in the second linear liquid 4 outside the region where the first parallel line pattern 3 is formed is used as the adjustment for satisfying the above formula (1). The angle is set to 6° or less.

Here, the contact angle outside the formation region of the first parallel line pattern 3 can be regarded as the substrate 1 at the region where the first linear liquid 2 for forming the first parallel line pattern 3 is not provided. Contact angle.

The measurement of the contact angle can be carried out using a contact angle measuring device DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. In the fifth form, The contact angle is a value obtained after the solvent having the highest boiling point among the solvents in the second linear liquid 4 is dropped, and the elapsed time is 5 seconds.

By setting the contact angle to 6° or less, the change in the wettability with respect to the second linear liquid 4 in the inner and outer regions of the formation region of the first parallel line pattern 3 can be reduced, and the second parallel can be made. At the line pattern 5, the interval between the line segments 51, 52 satisfies the above formula (1).

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

In the sixth embodiment, the liquid application amount per unit length of the second linear liquid 4 in the region where the first parallel line pattern 3 is formed is used as the adjustment for satisfying the above formula (1). The liquid application amount per unit length of the second linear liquid 4 outside the formation region of the parallel line pattern 3 is different from each other.

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

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

In this way, it is possible to prevent the first parallel line pattern 3 In the formation region, the interval between the line segments 51 and 52 of the second parallel line pattern 5 is more expanded or narrowed than the outside of the formation region.

The difference in the amount of liquid to be applied to the inside and outside of the region in which the first parallel line pattern 3 is formed can be appropriately adjusted so as to satisfy the formula (1). For example, when the inkjet method is used in the formation of the second linear liquid 4, the number of droplets discharged per unit length of the second linear liquid 4 or the droplets of each droplet can be used. The capacity is different from each other in the region where the first parallel line pattern 3 is formed, and the difference in the amount of liquid to be applied is set.

In the seventh aspect, the adjustment of the above formula (1) is performed, and after the first parallel line pattern 3 is formed, the formation of the first parallel line pattern 3 is included before the second linear liquid 4 is applied. The area within the area is washed.

As described above, in the region between the line segments 31, 32 in the formation region of the first parallel line pattern 3, there is a slight loss of the coffee stain (Coffee Stain) which is not transported to the line segment. The case of some of the components of the first linear liquid 2 at the positions of 31 and 32. Such a residual component may cause the interval between the line segments 51 and 52 constituting the second parallel line pattern 5 to be uneven.

The so-called washing can also represent the removal of such residual components. At this time, depending on the washing conditions, for example, depending on the type of the washing or the setting of the strength, it is affected by how much the residual component is removed. With this relationship, the difference in wettability of the second linear liquid 4 at the inner and outer portions of the region where the first parallel line pattern 3 is formed can be eliminated. In a certain aspect, the cleaning may be performed so as to remove residual components so that the interval between the line segments 51 and 52 constituting the second parallel line pattern 5 satisfies the above formula (1). . In this sense, washing can be defined as an example of the adjustment to satisfy the above formula (1).

The cleaning may be performed only in the formation region of the first parallel line pattern, or in the formation region including the first parallel line pattern and the region outside the formation region. It is also preferable if the substrate 1 is completely washed.

When the cleaning is performed only in the formation region of the first parallel line pattern, for example, it is possible to irradiate electromagnetic waves or the like in a state where the formation region is shielded, or to use an inkjet method. The cleaning solvent is selectively imparted into the formation region.

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

As a washing method by heating, there is a continuous heating method by an infrared heater, an oven, a hot plate, or the like, or an instantaneous heating method by a xenon flash lamp or the like. The heating conditions (temperature, time, etc.) are suitably set so that the interval between the line segments 51, 52 constituting the parallel line pattern 5 satisfies the above formula (1). When the substrate 1 is a film or the like, it is set so as not to make the base It is desirable to have a range of conditions in which the material 1 is deformed. In this point of view, it is preferred to carry out the heating by an instant, in particular, by a xenon flash lamp having less damage to a substrate such as a film.

As the electromagnetic wave, a method of irradiating an electron beam, a gamma line, an ultraviolet ray or the like can be used. The irradiation condition of the electromagnetic wave is suitably set so that the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above formula (1).

The solvent to be used in the cleaning by the solvent is not particularly limited as long as it satisfies the above formula (1). However, it is preferred to select a parallel for the deposition of the functional material. The effect of the line pattern is small. The solvent suitable for washing can be selected in accordance with the type of functional material. For example, when the water is dispersed in the form of silver nanoparticles, an ethanol-based solvent or the like is suitable.

The cleaning condition by the plasma can be suitably set within a range in which the interval between the line segments 51, 52 constituting the parallel line pattern 5 satisfies the above formula (1).

Next, the liquid containing the functional material discharged from the droplet discharge device will be described in detail.

The liquid containing the functional material discharged from the droplet discharge device is preferably a content of the functional material in a range of 0.01% by weight or more and 1% by weight or less. The above-mentioned "liquid containing a functional material discharged from the droplet discharge device" may be a liquid containing a functional material just before being dried on the substrate. By setting the content of the functional material to a range of 0.01% by weight or more and 1% by weight or less, The effect of making the formation of the parallel line pattern more stable is obtained.

The functional material contained in the liquid is not particularly limited as long as it is a material for imparting a specific function to the substrate. When a specific function is given, for example, when the conductivity is imparted to the substrate, the conductive material is used as a functional material, and when the insulating property is imparted, the insulating material is used as a function. Use materials to use. As the functional material, for example, a conductive material such as conductive fine particles or a conductive polymer, an insulating material, a semiconductor material, an optical filter material, a dielectric material or the like can be preferably exemplified. In particular, it is preferred that the functional material be a conductive material or a conductive material precursor. The conductive material precursor refers to a material that can be changed to a conductive material by applying a suitable treatment.

That is, the pattern forming method of the present invention is particularly suitable for use when forming a pattern composed of thin wires (line segments) containing a conductive material.

As the conductive material, for example, conductive fine particles, a conductive polymer, or the like is preferably exemplified.

The conductive fine particles are not particularly limited, but may preferably be, for example, Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, In the case of using fine particles of Mn, Ge, Sn, Ga, and In, in the case of using metal fine particles such as Au, Ag, and Cu, it is possible to form a circuit pattern having low electric resistance and high corrosion resistance. . From the viewpoint of cost and stability, it is preferable to use metal particles containing Ag. Some of these The average particle diameter of the metal fine particles is preferably in the range of 1 to 100 nm, and more preferably in the range of 3 to 50 nm.

Further, it is also preferable to use the carbon fine particles as the conductive fine particles. As the carbon fine particles, graphite fine particles, carbon nanotubes, fullerenes and the like are preferably exemplified.

The conductive polymer is not particularly limited, and a π-conjugated conductive polymer is preferably exemplified.

The π-conjugated conductive polymer is not particularly limited, and polythiophenes, polypyrroles, polyfluorenes, polycarbazoles, polyanilines, polyacetylenes, and polyfurans can be used. A chain-like conductive polymer such as polyparaphenylene, polyparaphenylene acetylene, polyparaphenylene sulfide, polyfluorene, polyisothianaphthene or polysulfurnitride. Among them, polythiophenes or polyanilines are preferred from the viewpoint of obtaining high conductivity. It is also most desirable to use poly(ethylene dioxythiophene).

The conductive polymer used in the present invention is more preferably formed by including the above-described π-conjugated conductive polymer and polyanion. Such a conductive polymer can be easily produced by chemically oxidizing a precursor of a π-conjugated conductive polymer precursor in the presence of a suitable oxidizing agent, an oxidation catalyst, and a polyanion. .

Polyanion, substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimine, substituted or unsubstituted polyamine, substituted or unsubstituted Polyester and copolymers thereof, which are composed of an anionic group and have no yin The constituent unit of the ionic group.

This polyanion is a solubilized polymer in which a π-conjugated conductive polymer is solubilized in a solvent. Further, the anion group of the polyanion acts as a dopant for the π-conjugated conductive polymer, and enhances the conductivity and heat resistance of the π-conjugated conductive polymer.

The anion group of the polyanion may be a functional group capable of inducing chemical oxidation doping of the π-conjugated conductive polymer, but from the viewpoint of easiness of production and stability, - A substituted sulfate group, a -substituted phosphate group, a phosphate group, a carboxyl group, a sulfo group or the like is preferred. Further, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a -substituted sulfate group or a carboxyl group is more preferable.

Specific examples of the polyanion include polyvinylsulfonic acid, polystyrenesulfonic acid, polyarylsulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, and poly-2-propenylamine. -2-methylpropanesulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyaryl carboxylic acid, polypropylene carboxylic acid, polymethacrylic carboxylic acid, poly 2-propenylamine-2-methylpropanesulfonic acid, polyisoprenecarboxylic acid, polyacrylic acid, and the like. It may be a single polymer for this purpose, or may be a copolymer of two or more types.

Further, it may be a polyanion having F (fluorine atom) in the compound. Specifically, the product includes a NAFION (manufactured by Dupont Co., Ltd.) containing a perfluorosulfonic acid group, and FLEMION (manufactured by Asahi Glass Co., Ltd.) made of a perfluorovinyl ether containing a carboxylic acid group.

Among these, if it is a compound having a sulfonic acid, then When the inkjet printing method is used, the ink emission stability is particularly good, and high conductivity can be obtained, which is more preferable.

Further, among these, polystyrenesulfonic acid, polyisoprenesulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions exhibit an excellent electrical conductivity.

The degree of polymerization 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.

Conductive polymers are also ideally available from commercially available materials. For example, a conductive polymer made of poly(3,4-dioxyethylene thiophene) and polystyrene sulfonic acid (abbreviated as PEDOT/PSS) is marketed by HC Starck as the CLEVIOS series. It is marketed by Aldrich as PEDOT-PASS483095, 560598, and sold by Nagase Chemtex as the Denatron series. Further, polyanion is marketed by Nissan Chemical Co., Ltd. as an ORMECON series.

As the liquid containing a functional material, one type or two or more types of water and an organic solvent may be used in combination.

The organic solvent is not particularly limited, and examples thereof include 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-. Alcohols such as butanediol and propylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol mono An ether such as a group ether or a dipropylene glycol monoethyl ether or the like.

Also, as a liquid containing a functional material, it is not damaged. Further, in the range of the effects of the present invention, various additives such as a surfactant may be contained.

By using a surfactant, for example, when it is desired to form the linear liquid 2 by using a droplet discharge device, it is possible to adjust the surface tension or the like to achieve the stabilization of discharge. The surfactant is not particularly limited, but a lanthanoid surfactant or the like can be used. The lanthanide surfactant is a polyether-denatured one which has a side bond or a terminal of a polydimethyl oxyalkanic acid. For example, on the market, KF-351A and KF-made by Shin-Etsu Chemical Co., Ltd. are sold. 642 or BYK347, BYK348, etc. made by BYK. The amount of the surfactant to be added is preferably 1% by weight or less based on the total amount of the liquid forming the linear liquid 2.

The substrate is not particularly limited, but examples thereof include glass and plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic resin, polyester). , polyamine, etc.), metal (copper, nickel, aluminum, iron, etc., or alloy), ceramics, etc., these may be used alone or in a bonded state. Among them, plastic is ideal, and polyethylene terephthalate, polyethylene, polypropylene, and the like are suitable.

Figure 29 is a partially omitted perspective view showing an example of a parallel line pattern formed on a substrate, the section corresponding to the direction orthogonal to the direction in which the parallel line pattern is formed. Longitudinal section of the break.

Parallel line pattern 3 of 1 produced by linear liquid The group of 2 thin lines (line segments) 31, 32 is not absolutely necessary to be completely independent of each other. As shown in the figure, the two line segments 31, 32 are connected as a thin film portion 30 formed by covering the line segments 31, 32 by a lower height than the height of the line segments 31, 32. It is also ideal when a continuous body is formed.

The line widths W1 and W2 of the line segments 31 and 32 of the parallel line pattern 3 are preferably 10 μm or less. When it is 10 μm or less, since it is generally not visually recognizable, it is more preferable from the viewpoint of improving transparency. In consideration of the stability of each of the line segments 31 and 32, the line widths W1 and W2 of the respective line segments 31 and 32 are preferably in the range of 2 μm or more and 10 μm or less.

Further, the widths W1, W2 of the line segments 31, 32 are set to Z at the height of the thinnest portion of the thickness of the functional material between the line segments 31, 32, and further from the Z When the protruding heights of the line segments 31 and 32 are set to Y1 and Y2, they are defined as the width of the line segments 31 and 32 at the height of one half of Y1 and Y2. For example, when the parallel line pattern 3 is provided with the above-described thin film portion 30, the height of the thinnest portion at the thin film portion 30 can be set to Z. Further, when the height of the thinnest portion of the functional material between the respective line segments 31, 32 is 0, the line widths W1, W2 of the line segments 31, 32 are defined as the line segments 31 from the surface of the substrate 1. The width of the line segments 31, 32 at the height of one of the heights H1, H2 of 32.

The line width of the line segments 31, 32 constituting the parallel line pattern 3 Since W1 and W2 are extremely thin as described above, the heights H1 and H2 of the line segments 31 and 32 from the surface of the substrate 1 are set to be smaller from the viewpoint of securing the cross-sectional area and reducing the resistance. High is ideal. Specifically, the heights H1 and H2 of the line segments 31 and 32 are preferably in the range of 50 nm or more and 5 μm or less.

Further, from the viewpoint of improving the stability of the parallel line pattern 3, it is preferable that the H1/W1 ratio and the H2/W2 ratio are each in a range of 0.01 or more and 1 or less.

Further, from the viewpoint of further thinning the parallel line pattern 3, the thickness of the functional material between the line segments 31, 32 becomes the height Z of the thinnest thinnest portion, specifically, the film. The height Z of the thinnest portion of the portion 30 is preferably in the range of 10 nm or less. It is preferable that the thin film portion 30 is provided in a range of 0 < Z ≦ 10 nm in order to achieve a good balance between transparency and stability.

Further, in order to achieve further thinning of the parallel line pattern 3, the H1/Z ratio and the H2/Z ratio are preferably 5 or more, and each of 10 or more is more desirable, and each of them is 20 or more is particularly desirable.

The range of the arrangement interval I of the line segments 31 and 32 is not particularly limited. As described with reference to FIGS. 17 to 19, in general, when a linear liquid is formed, a plurality of nozzles are provided by a pixel group which is arranged in parallel with respect to a nozzle row of the droplet discharge device. The droplet group is given as a complex array in a direction intersecting the nozzle row, and the droplets of the complex array are combined into one, and formed in a line intersecting the nozzle row The linear liquid extending in the direction can be appropriately set with respect to the arrangement interval I with a high degree of freedom, and particularly when the arrangement interval I is increased, the bulging can be appropriately prevented. Specifically, even when the arrangement interval I is set to, for example, a value of 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, or 500 μm or more, the bulging can be appropriately prevented. The formation of the line segments 31, 32 is stabilized. In a state where the bulging is appropriately prevented, the arrangement interval I can be appropriately set to an optimum value depending on the use. In the case of forming a transparent conductive film or the like, the interval I is preferably in the range of 10 μm or more to 1000 μm or less, and more preferably in the range of 10 μm or more to 500 μm or less. Further, it is also preferable to arrange the interval I in the range of 10 μm or more and 300 μm or less.

Further, the arrangement interval I between the line segments 31 and 32 is the distance between the largest projections of the line segments 31 and 32.

Further, it is preferable to apply the same shape (the same sectional area) to the line segment 31 and the line segment 32. Specifically, it is preferable to set the heights H1 and H2 of the line segment 31 and the line segment 32 as substantial. Is equal value. Similarly, the line widths W1 and W2 for the line segment 31 and the line segment 32 are also ideally set to be substantially equal.

The line segments 31, 32 are not absolutely required to be parallel, as long as at least a certain length L of the line segment direction is covered and the line segments 31, 32 are not combined with each other. Preferably, at least a certain length L of the direction of the line segment is covered, and the line segments 31, 32 are substantially parallel to each other.

The length L of the line segments 31 and 32 in the line segment direction is preferably five times or more the arrangement interval I of the line segments 31 and 32, and more preferably 10 times or more. The length L and the arrangement interval I can be set corresponding to the formation length of the pattern (linear liquid) 2 and the formation of the width.

At the starting point and the end point of the formation of the linear liquid (the starting point and the end point of a certain length L covering the direction of the line segment), the line segments 31, 32 may be connected to each other and formed as a continuous body.

Further, the line segments 31 and 32 are preferable, and the line widths W1 and W2 are slightly equal, and the line widths W1 and W2 are sufficiently thinner than the distance between the two lines (arrangement interval I). .

Further, the line segment 31 and the line segment 32 constituting the pattern 3 which are generated by one linear liquid are preferably formed at the same time.

The parallel line pattern 3 is particularly preferable, and each of the line segments 31 and 32 satisfies all of the following conditions (A) to (C). Thereby, the pattern becomes difficult to be visually recognized, and transparency can be improved, and the line segment can be stabilized, especially when the functional material is a conductive material, and the pattern can be made. Excellent effect of lowering the resistance value.

(A) When the heights of the respective line segments 31 and 32 are H1 and H2, and the height of the thinnest portion between the line segments is Z, it is 5≦H1/Z and is 5≦H2/ Z.

(B) When the width of each of the line segments 31 and 32 is W1 and W2, it is W1 ≦ 10 μm and W2 ≦ 10 μm.

(C) When the heights of the respective line segments 31 and 32 are set to H1 and H2, It became 50 nm < H1 < 5 μm and 50 nm < H2 < 5 μm.

The above description for the parallel line pattern 3 can also be applied to the parallel line pattern 5.

In the above description, the inclination angle θ with respect to the direction in which the linear liquid is formed in the relative movement direction D of the liquid droplet ejection device for the substrate is mainly made for the case of 45° and the case of -45°. Shown, but the invention is not limited thereto. The direction in which the linear liquid is formed may be set to an arbitrary inclination angle as long as it is not a direction parallel to the relative movement direction D and is not a direction orthogonal to the relative movement direction D.

In the above description, the pattern formed as the final is mainly described as an example of a pattern in which a grid pattern formed by parallel line patterns is formed, but is not limited thereto. According to the present invention, the linear liquid is formed by a direction which is inclined with respect to the relative moving direction D of the liquid droplet discharging device for the substrate, and the pattern is formed when various patterns including the parallel line pattern are formed. The degree of freedom of the system is enhanced. Therefore, when various patterns are formed, free patterning can be performed, and the prevention of corrugation and the improvement of surface pick-up efficiency can be achieved. Further, it is possible to reduce the burden of resetting the arrangement angle of the ink jet head and the substrate, and it is possible to improve productivity.

A transparent conductive film substrate is attached to the surface of the substrate, and is provided with a transparent conductive film including a pattern formed by the pattern forming method described above. a transparent conductive film, even when the functional material (conductive material) contained therein is not transparent, by using a linear liquid The volume change is a parallel line pattern and is thinned, and the pattern can be made difficult to be visually recognized.

The use of the transparent conductive film substrate is not particularly limited, but can be used as various devices included in various electronic devices.

The use of the transparent conductive film substrate of the present invention is preferably used as a display for various types such as liquid crystal, plasma, organic electric field emission, and field emission, from the viewpoint of exhibiting the effects of the present invention remarkably. The transparent electrode is suitably used as a transparent electrode used in a touch panel or a mobile phone, an electronic paper, various solar cells, various electric field light-emitting dimming elements, and the like.

More specifically, the transparent conductive film substrate of the present invention is suitably used as a transparent electrode of a device. The device is not particularly limited, and, for example, a touch panel or the like can be suitably exemplified. In addition, the electronic device including such a device is not particularly limited, and, for example, a smart phone, a tablet terminal, or the like can be suitably exemplified.

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

[Examples]

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

1. Pattern forming method

(Example 1)

<Substrate>

As the substrate, a PET substrate to which a surface treatment was applied so that the contact angle of the liquid containing the functional material was 20.3° was prepared. As the surface treatment, a corona discharge treatment was performed using "PS-1M" manufactured by Shinko Electric Co., Ltd.

<droplet discharge device>

An inkjet head of "KM1024iLHE-30" (standard droplet capacity: 30 pL) manufactured by KONICA MINOLTA Co., Ltd. was prepared as a droplet discharge device.

<Ink composition>

As the ink (liquid containing a functional material), the following components are formulated.

‧ Silver nanoparticles (average particle size: 20 nm): 0.16 wt%

‧Interactive surfactant ("BYK-348" by BYK): 0.05wt%

‧ Diethylene glycol monobutyl ether (abbreviation: DEGBE) (dispersion medium): 20wt%

‧Water (dispersive medium): residual

<Formation of patterns>

While the droplet discharge device is relatively moved relative to the substrate, the ink is ejected from a plurality of nozzles of the droplet discharge device, and the X-axis direction is inclined at 45° with respect to the relative movement direction D. To form a linear liquid. At this time, the relative movement direction D is a direction along the width direction of the substrate.

By linearly evaporating and drying the linear liquid along the X-axis direction, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the X-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

Then, while the droplet discharge device is relatively moved with respect to the substrate, ink is ejected from a plurality of nozzles of the droplet discharge device, and is inclined at -45° with respect to the relative movement direction D. In the Y-axis direction, a linear liquid is formed. Here, the Y-axis direction is a direction orthogonal to the X-axis direction described above.

By linearly evaporating and drying the linear liquid along the Y-axis direction, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the Y-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

In the pattern formation described above, when the linear liquid along the X-axis direction is applied and the linear liquid along the Y-axis direction is applied, the relative arrangement of the droplet discharge device with respect to the substrate is not provided. Angle change more. In other words, when a linear liquid along the X-axis direction is applied and a linear liquid along the Y-axis direction is applied, the relative movement direction D of the droplet discharge device with respect to the substrate is the same. Along the direction of the width direction of the substrate.

As described above, a grid-like pattern in which parallel line patterns along the X-axis direction and parallel line patterns along the Y-axis direction intersect each other is formed.

In the above pattern formation, the ink discharge by the droplet discharge device when forming the linear liquid along the X-axis direction and the linear liquid along the Y-axis direction is controlled as follows. .

<Ink discharge control>

‧ unit droplet volume per droplet V _d = 30 [pL]

‧degree N=8[dpd]

‧ Total droplet capacity V (= V _d [pL] × N [dpd]) = 240 [pL] discharged from one nozzle to form one linear liquid

‧Nozzle column resolution R=360[npi]

‧Production V‧R=8.64×10 ⁴ [pL‧npi]

‧ Maximum discharge time difference Δt _max = 81.0 [ms] of liquid containing functional material discharged from nozzles adjacent to each other in order to form one linear liquid

‧The interval of the linear liquid imparted by one pass is M _p =797.6 [μm]

‧The interval between the linear liquids finally given is M=398.8 [μm]

‧ total number of passes

The number of passes when forming a linear liquid along the X-axis direction is set to 2, and the number of passes when forming a linear liquid along the Y-axis direction is set to 2 times.

The total number of passes for the total number of passes for this is 4 times. For the given interval M for consideration by a liquid line followed by the given interval M _p imparting and ultimately granted in the liquid line, set by the number.

(Example 2)

In the first embodiment, as the substrate, a PET substrate to which a surface treatment is applied so that the contact angle of the liquid containing the functional material is 8.7° is used, and the first embodiment is the same as that of the first embodiment. The same pattern is formed. The surface treatment is a corona discharge treatment using "PS-1M" manufactured by Shinko Electric Co., Ltd., which is the same as in the first embodiment, but the treatment intensity is adjusted so as to become the contact angle. .

(Example 3)

In the first embodiment, as the substrate, a PET substrate to which a surface treatment is applied so that the contact angle of the liquid containing the functional material is 10.4° is used, and the first embodiment is the same as that of the first embodiment. The same pattern is formed. The surface treatment is a corona discharge treatment using "PS-1M" manufactured by Shinko Electric Co., Ltd., which is the same as in the first embodiment, but the treatment intensity is adjusted so as to become the contact angle. .

(Example 4)

In the first embodiment, as the substrate, a PET substrate to which a surface treatment is applied so that the contact angle of the liquid containing the functional material is 29.7° is used, and the first embodiment is the same as that of the first embodiment. The same pattern is formed. The surface treatment is a corona discharge treatment using "PS-1M" manufactured by Shinko Electric Co., Ltd., which is the same as in the first embodiment, but the treatment intensity is adjusted so as to become the contact angle. .

(Example 5)

In the first embodiment, as the substrate, a PET substrate to which a surface treatment is applied so that the contact angle of the liquid containing the functional material is 32.3° is used, and the first embodiment is the same as that of the first embodiment. The same pattern is formed. The surface treatment is a corona discharge treatment using "PS-1M" manufactured by Shinko Electric Co., Ltd., which is the same as in the first embodiment, but the treatment intensity is adjusted so as to become the contact angle. .

(Example 6)

In the first embodiment, the gradation N is changed to 3 [dpd>, and the product V‧R is set to 3.24 × 10 ⁴ [pL ‧ npi].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.42% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

Except for the above points, the same shape as in the first embodiment Become a pattern.

(Example 7)

In the first embodiment, the gradation N is changed to 4 [dpd>, and the product V‧R is set to 4.32 × 10 ⁴ [pL ‧ npi].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.32% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

A pattern was formed in the same manner as in Example 1 except for the above points.

(Example 8)

In the first embodiment, the gradation N is changed to 12 [dpd>, and the product V‧R is set to 1.30 × 10 ⁵ [pL ‧ npi].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.11% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

A pattern was formed in the same manner as in Example 1 except for the above points.

(Example 9)

In the first embodiment, the gradation N is changed to 16 [dpd>, and the product V‧R is set to 1.73 × 10 ⁵ [pL ‧ npi].

Further, the concentration of the silver nanoparticles in the ink is adjusted. It is 0.08 wt%. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

A pattern was formed in the same manner as in Example 1 except for the above points.

(Embodiment 10)

In the first embodiment, the pattern was formed in the same manner as in the first embodiment except that the moving speed of the ink jet head was changed and the maximum discharge time difference Δt _{max was} 101.3 [ms].

(Example 11)

In the first embodiment, the pattern was formed in the same manner as in the first embodiment except that the moving speed of the ink jet head was changed and the maximum discharge time difference Δt _{max was} 192.4 [ms].

(Embodiment 12)

In the first embodiment, the pattern was formed in the same manner as in the first embodiment except that the moving speed of the ink jet head was changed and the maximum discharge time difference Δt _{max was} 222.8 [ms].

(Example 13)

In the first embodiment, the application interval M _p of the linear liquid to be supplied by one pass is set to 398.8 [ms], and the total number of passes is set to two times. 1 is identical and a pattern is formed.

Here, the number of passes when forming a linear liquid along the X-axis direction is once, and the number of passes when forming a linear liquid along the Y-axis direction is also set to one time. The total number of passes is set to 2 times.

(Example 14)

In the first embodiment, the application interval M _p of the linear liquid to be supplied by one pass is set to 1196.4 [ms], and the total number of passes is set to six times. 1 is identical and a pattern is formed.

Here, the number of passes when the linear liquid is formed along the X-axis direction is set to three times, and the number of passes when the linear liquid is formed along the Y-axis direction is also set to three times. The total number of passes is set to 6 times.

(Example 15)

In the first embodiment, the gradation N is changed to 32 [dpd>, and the product V‧R is set to 3.45 × 10 ⁵ [pL ‧ npi]. And, along with the expansion of the line width of two lines, the line followed by a liquid through the given interval M _p imparting change 1595.2 [μm], and finally imparting linear conferred liquid The interval M was changed to 797.6 [μm].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.04% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

(Embodiment 16)

In the first embodiment, the gradation N is changed to 48 [dpd>, and the product V‧R is set to 5.18 × 10 ⁵ [pL ‧ npi]. And, along with the expansion of the line width of two lines, the line followed by a liquid through the given interval M _p imparting change 1595.2 [μm], and finally imparting linear conferred liquid The interval M was changed to 797.6 [μm].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.027% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

(Example 17)

In the first embodiment, the gradation N is changed to 54 [dpd>, and the product V‧R is set to 5.83 × 10 ⁵ [pL ‧ npi]. And, along with the expansion of the line width of two lines, the line followed by a liquid through the given interval M _p imparting change 1595.2 [μm], and finally imparting linear conferred liquid The interval M was changed to 797.6 [μm].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.024% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid is set to a value close to that of the first embodiment.

(Embodiment 18)

In the first embodiment, when a linear liquid is formed, as described with reference to FIGS. 17 to 19, a plurality of nozzles are arranged for the pixel groups arranged in parallel with respect to the nozzle row of the droplet discharge device. The set of droplets is given as a complex array in a direction intersecting the nozzle row, and the droplets of the complex array are combined into one, and formed in a line extending in a direction crossing the nozzle row liquid. Specifically, the number of pixels (the number of adjacent pixels) constituting the pixel group in the nozzle row direction is set to 2. Further, the gradation N is set to 4 [dpd]. The product V‧R is set to 8.64 × 10 ⁴ [pL‧npi].

(Embodiment 19)

In the eighteenth embodiment, the number of pixels constituting the pixel group in the nozzle row direction is set to eight. Further, the gradation N is set to 6 [dpd]. The product V‧R is set to 5.18 × 10 ⁵ [pL‧npi]. And, along with the expansion of the line width of two lines, the line followed by a liquid through the given interval M _p imparting change 1595.2 [μm], and finally imparting linear conferred liquid The interval M was changed to 797.6 [μm].

Further, the concentration of the silver nanoparticles in the ink was adjusted to 0.027% by weight. By this, the amount of silver nanoparticles imparted per unit length of the linear liquid was set to a value close to that of Example 18.

(Comparative Example 1)

The composition of the substrate, the droplet discharge device, and the ink used in Comparative Example 1 was the same as in Example 1.

In Comparative Example 1, pattern formation was carried out as follows.

<Formation of patterns>

While the droplet discharge device is relatively moved relative to the substrate, the ink is continuously discharged from the nozzle of the droplet discharge device, and the body is in the X-axis direction in the same direction as the relative movement direction D. A linear liquid is formed. At this time, the relative movement direction D is a direction along the width direction of the substrate.

By linearly evaporating and drying the linear liquid along the X-axis direction, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the X-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

Next, the substrate was rotated by 90° with respect to the droplet discharge device, and the arrangement angle of the relative position of the droplet discharge device with respect to the substrate was changed. That is, the relative moving direction of the droplet discharge device with respect to the substrate is changed. Therefore, the relative movement direction D of the droplet discharge device after the change corresponds to the direction in which the parallel line pattern formed before is formed, that is, the direction orthogonal to the X-axis direction, that is, corresponds to In the Y-axis direction. The relative movement direction D after the configuration is changed is the direction along the longitudinal direction of the substrate.

After the arrangement is changed as described above, the droplet discharge device moves relative to the substrate, and the ink is ejected from the nozzle of the droplet discharge device, and the body is moved in the relative direction. D is in the Y direction of the same direction to form a linear liquid.

By evaporating and drying the linear liquid along the Y-axis direction Drying, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the Y-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

As described above, a grid-like pattern in which parallel line patterns along the X-axis direction and parallel line patterns along the Y-axis direction intersect each other is formed.

In the above pattern formation, the ink discharge by the droplet discharge device when forming the linear liquid along the X-axis direction and the linear liquid along the Y-axis direction is controlled as follows. .

<Ink discharge control>

‧ unit droplet volume per droplet V _d = 30 [pL]

‧degree N=8[dpd]

‧The interval of the linear liquid imparted by one pass is M _p =797.6 [μm]

‧The interval between the linear liquids finally given is M=398.8 [μm]

‧ total number of passes

The number of passes when forming a linear liquid along the X-axis direction is set to 2, and the number of passes when forming a linear liquid along the Y-axis direction is set to 2 times.

The total number of passes for the total number of passes for this is 4 times.

2. Evaluation method

The pattern properties and the physical property values were evaluated for the patterns formed by the respective examples and comparative examples.

(1) Pattern properties

As the pattern property, the following items (bulk prevention, width of two lines, and width of fine lines) were evaluated.

‧ bulging prevention

The properties of the two lines shown in Tables 1 to 5 are observed by optical microscopy for one set of two thin lines and 50 mm in the direction of thin line formation, and are based on the following evaluation criteria. The bulging prevention was evaluated.

<Evaluation criteria>

A: No bulging

B: Bulging occurred (3 or less)

C: bulging occurred (more than 4 places)

‧2 line width

The line width (μm) of the two lines is measured by an optical microscope to measure the interval between two sets of two thin lines. The measured value corresponds to the above interval I.

‧ Thin line width

The width (μm) of the thin line is measured by the optical microscope to measure the width of one set of two thin lines. The measured values correspond to the above-described wide widths W1 and W2. Further, since the widths of the two thin wires are substantially the same, the measured value of one of the thin wires is taken as the fine line width (μm).

(2) Physical property value

The physical property values were evaluated for the following items (transmittance, sheet resistance, and terminal resistance).

‧Transmission rate (total light transmittance)

The transmittance (total light transmittance) (%T) is the total light transmittance measured by AUTOMATICHAZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku Co., Ltd. In addition, the correction was performed using a substrate having no pattern, and the total light transmittance of the formed pattern was measured.

‧Sheet resistance

The sheet resistance (Ω/□) was measured using a Loresta-EP (MODEL MCP-T360 type) tandem 4-probe probe (ESP) manufactured by DIA INSTRUMENTS.

Before the above measurement, the substrate was heated by heating on a hot plate at 120 ° C for 1 hour, and a heat baking treatment was applied to the pattern.

‧Terminal resistance

The terminal resistance (Ω) is a pattern formed in a short-shaped area of 100 mm × 5 mm, and the resistance value between the terminals (that is, between the both ends in the longitudinal direction of the short-handed area) is measured. The value.

Before the above measurement, the substrate was heated by heating on a hot plate at 120 ° C for 1 hour, and a heat baking treatment was applied to the pattern.

3. Evaluation

(1) Influence of contact angle

The results of Examples 1 to 5 are shown in Table 1. Examples 1 to 5 are those in which the contact angle of the liquid containing the functional material is different.

According to Table 1, it can be seen that if the contact angle is in the range of 10 [°] or more and 30 [°] or less, the effect of further improving the transparency of the formed parallel line pattern can be obtained.

In addition, when the contact angle is in the range of 10 [°] or more and 30 [°] or less, the linear liquid system is more easily formed linearly, and bulge can be appropriately prevented. occur. As a result, it has been found that the line segments constituting the parallel line pattern formed are more easily formed linearly, and the occurrence of disconnection can be appropriately prevented. Therefore, it has been found that when a conductive material is used as a functional material, the following effects can be obtained: that is, the sheet resistance and the terminal resistance of the obtained pattern can be further improved. improve.

(2) The impact of the product V‧R

The results of Examples 1, 6-9, and 15-17 are shown in Table 2. In the first, sixth, and fifth to fifth embodiments, the total liquid droplet capacity V and the nozzle column resolution R, which are supplied from one nozzle, are used to form a linear liquid. Different. Specifically, the product V‧R is changed by the adjustment of the gradation N. In addition, the amount of silver nanoparticles imparted per unit length of the linear liquid is adjusted to a value similar to that of the first embodiment by adjusting the concentration of the silver nanoparticles in the ink.

According to Table 2, it can be seen that if the product V‧R[pL‧npi] is in the range of 4.32 × 10 ⁴ [pL‧npi] or more and 5.18 × 10 ⁵ [pL‧npi] or less, the linear liquid system becomes more It is easy to be formed linearly, and bulging can be appropriately prevented. As a result, it has been found that the line segments constituting the parallel line pattern formed are more easily formed linearly, and the occurrence of disconnection can be appropriately prevented. Therefore, it has been found that when a conductive material is used as a functional material, the following effects can be obtained: that is, the sheet resistance and the terminal resistance of the obtained pattern can be further improved. improve.

(3) Influence of maximum discharge time difference Δt _max

The results of Examples 1, 10 to 12 are shown in Table 3. In the first and third embodiments, the maximum discharge time difference Δt _max of the liquid containing the functional material discharged from the nozzles adjacent to each other in order to form one linear liquid is different.

According to Table 3, it is understood that the effect of appropriately improving the terminal resistance can be obtained by controlling the maximum discharge time difference Δt _max to 200 [ms] or less.

(4) Effect of the interval M _p of the linear liquid

The results of Examples 1, 13, and 14 are shown in Table 4. Examples 1, 13, and 14 are those in which the interval M _p of the linear liquid imparted by the passage of one pass is different. Followed by a response to the imparted by imparting linear interval M of the _P liquid, and so as to impart linear interval M can be achieved in the liquid given final, set by the number.

According to Table 4, it is possible that, by 1 followed by the line of the liquid by imparting given interval M _p is set to 400 [μm] or more, of the liquid during the drying wire, can be based on the accompanying The effect of the vapor generated by the drying of the adjacent linear liquid is reduced, and an effect of making the formation of the parallel line pattern more stable can be obtained. As a result, it was found that an effect of further improving the bulging prevention property and the transparency can be obtained. Further, it can be seen that if the functional material is a conductive material, it is possible to obtain an effect of further improving the sheet resistance and the terminal resistance of the obtained pattern.

(5) The influence of the number of adjacent pixels

The results of Examples 1, 18, and 19 are shown in Table 5. In the first embodiment, when a linear liquid is formed, the liquid droplets given from one nozzle for one pixel are given in plural in the direction intersecting the nozzle row, and the plural is given. The droplets are combined into one to form a linear liquid extending in a direction crossing the nozzle row. On the other hand, in the examples 18 and 19, when the linear liquid is formed, the droplets are given from the plurality of nozzles to the pixel group arranged in parallel with respect to the nozzle row of the droplet discharge device. The group is provided as a complex array in a direction intersecting the nozzle row, and the droplets of the complex array are combined to form a linear liquid extending in a direction intersecting the nozzle row. The number of pixels (the number of adjacent pixels) constituting the pixel group in the nozzle row direction is set to 1 in the first embodiment, 2 in the embodiment 18, and 8 in the nineteenth embodiment.

According to Table 5, it can be understood that the effect of the present invention can be exhibited even when the number of adjacent pixels is plural. Further, as shown in the results of Example 19, even when the amount of droplets per unit length of the linear liquid is large, that is, the product of the gradation N [dpd] and the number of adjacent pixels is In the case of a large case, it is also possible to appropriately suppress the increase in the maximum discharge time difference Δt _max [ms]. In the tenth embodiment, the maximum discharge time difference Δt _max [ms] is greatly shortened compared to the maximum discharge time difference Δt _max [ms] of the embodiment 16 which is equivalent to the droplet application amount. The bulging prevention system is further improved. As a result, it was found that an effect of further improving the sheet resistance and the terminal resistance of the obtained pattern can be obtained.

(6) Comparison of examples and comparative examples

Further, the results of Example 1 and Comparative Example 1 are shown in Table 6.

According to Table 6, it can be seen that in the first embodiment in which the linear liquid is formed obliquely with respect to the relative movement direction of the liquid droplet ejection device and the substrate, it is not necessary to perform X as in Comparative Example 1. The change in the substrate arrangement at the time of forming the shaft and the Y-axis pattern can improve the productivity.

Further, in Comparative Example 1, since the relative movement direction D of the droplet discharge device is set to the direction along the side of the substrate, the prevention of the corrugation and the improvement of the surface extraction efficiency cannot be simultaneously achieved.

Further, in Example 1, according to comparison with Comparative Example 1, it was found that it was also excellent in bulging prevention property. Further, it can be seen that if the functional material is a conductive material, it is possible to obtain an effect of improving the sheet resistance and the terminal resistance of the obtained pattern.

(Embodiment 20)

1. Modulation of ink

The ink 1 composed of the following composition was prepared.

‧ Silver nanoparticle aqueous dispersion 1 (silver nanoparticle: 40% by weight): 1.75 wt%

‧矽 surfactant (BYK-348 by BYK): 0.01% by weight

‧Pure water: Residue

2. Modulation of the substrate

As a substrate, it is used by easy processing (surface treatment) The substrate 1 made of a PET substrate having a surface energy E of 52 mN/m.

3. Determination of surface energy and contact angle

Before the formation of the grid-like functional pattern, the surface energy in the formation region of the first parallel line pattern formed by the ink 1 and the contact angle of the second linear liquid are measured by a substitute method. .

(1) Determination of surface energy

On the substrate 1, 20 μL of the ink 1 was dropped and dried, and a ring-shaped fine line due to the phenomenon of coffee stain was formed around the droplets. Thereafter, the contact angles of water, propylene carbonate, and diiodomethane were measured for the central region inside the annular thin wire, and the surface energy was calculated according to the Young-Fowkes formula. Here, the measurement of the contact angle of water, propylene carbonate, and diiodomethane was carried out using a contact angle measuring apparatus DM-501 manufactured by Kyowa Interface Chemical Co., Ltd. (in the measurement of the contact angle described below, the same is used. Device). The calculated surface energy value was 56 mN/m. This value is taken as the surface energy C in the formation region of the first parallel line pattern.

(2) Determination of the contact angle of the second linear liquid

A. Measurement of the contact angle of the second linear liquid in the formation region of the first parallel line pattern. The contact angle of the ink 1 is 22°, and the polyethylene terephthalate (PET) which is easily processed is processed. On the substrate, 20 μL of the ink 1 was dropped and dried, and a coffee was formed around the droplets. The ring-shaped thin line caused by the stain phenomenon. Thereafter, the contact angle of the ink 1 (the same composition as the second linear liquid) was measured for the central region inside the annular thin wire. The contact angle measured was 17°. This value is taken as the contact angle F of the second linear liquid in the formation region of the first parallel line pattern.

B. Measurement of the contact angle of the second linear liquid outside the formation region of the first parallel line pattern

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

4. Pattern formation

<droplet discharge device>

An inkjet head of "KM1024iLHE-30" (standard droplet capacity: 30 pL) manufactured by KONICA MINOLTA Co., Ltd. was prepared as a droplet discharge device.

<Formation of patterns>

While the droplet discharge device is relatively moved relative to the substrate, the ink is ejected from a plurality of nozzles of the droplet discharge device, and the X-axis direction is inclined at 45° with respect to the relative movement direction D. To form a linear liquid. At this time, the relative movement direction D is a direction along the width direction of the substrate.

By linearly evaporating and drying the linear liquid along the X-axis direction, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the X-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

Then, while the droplet discharge device is relatively moved with respect to the substrate, ink is ejected from a plurality of nozzles of the droplet discharge device, and is inclined at -45° with respect to the relative movement direction D. In the Y-axis direction, a linear liquid is formed. Here, the Y-axis direction is a direction orthogonal to the X-axis direction described above.

By linearly evaporating and drying the linear liquid along the Y-axis direction, the functional material is selectively deposited on the edge of the linear liquid to form a parallel line pattern along the Y-axis direction. Here, the drying of the linear liquid is promoted by patterning the substrate disposed on the stage heated to 70 °C.

In the pattern formation described above, when the linear liquid along the X-axis direction is applied and the linear liquid along the Y-axis direction is applied, the relative arrangement of the droplet discharge device with respect to the substrate is not provided. The angle is changed. In other words, when a linear liquid along the X-axis direction is applied and a linear liquid along the Y-axis direction is applied, the relative movement direction D of the droplet discharge device with respect to the substrate is the same. Along the direction of the width direction of the substrate.

As described above, a grid-like pattern in which parallel line patterns along the X-axis direction and parallel line patterns along the Y-axis direction intersect each other is formed.

In the above pattern formation, the ink discharge by the droplet discharge device when forming the linear liquid along the X-axis direction and the linear liquid along the Y-axis direction is controlled as follows. .

<Ink discharge control>

‧ unit droplet volume per droplet V _d = 30 [pL]

‧degree N=3[dpd]

‧ Total droplet capacity V (= V _d [pL] × N [dpd]) = 90 [pL] given from one nozzle to form one linear liquid

‧Nozzle column resolution R=360[npi]

‧Production V‧R=3.24×10 ⁴ [pL‧npi]

‧ Coating interval of linear liquid = 282 [μm]

‧ total number of passes

The number of passes when forming a linear liquid along the X-axis direction is once, and the number of passes when forming a linear liquid along the Y-axis direction is also set to 1 time.

In this manner, a functional pattern in a grid shape in which the first parallel line pattern and the second parallel line pattern intersect each other at right angles is formed. The overall size of the grid-like functional pattern is 50 mm × 50 mm.

(Example 21)

1. Modulation of ink

The ink 2 composed of the following composition was prepared.

‧ Silver nanoparticle particle dispersion 2 (silver nanoparticle: 40 weight Quantity%): 1.75 wt%

‧矽 surfactant (BYK-348 by BYK): 0.01% by weight

‧Pure water: Residue

Further, the aqueous dispersion 2 of the silver nanoparticles and the aqueous dispersion 1 of the silver nanoparticles used in Example 20 were different in dispersant.

2. Modulation of the substrate

As the substrate, the substrate 1 (surface energy E = 52 mN/m) was used.

3. Determination of surface energy and contact angle

The ink 1 of Example 20 was replaced with Ink 2, and was measured in the same manner as in Example 20. As a result, the surface energy C in the region where the first parallel line pattern was formed was 49 mN/m. The contact angle F of the second linear liquid in the region where the parallel line pattern is formed is 25°, and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is 21°.

4. Pattern formation

A functional pattern in the form of a grid was formed in the same manner as in Example 20 except that the ink 1 was replaced with the ink 2.

(Example 22)

1. Modulation of ink

As the ink, ink 1 is used.

2. Modulation of the substrate

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

3. Determination of surface energy and contact angle

The substrate 1 of Example 20 was replaced with the substrate 2, and was measured in the same manner as in Example 20. As a result, the surface energy C in the region where the first parallel line pattern was formed was 56 mN/m. The contact angle F of the second linear liquid in the region where the first parallel line pattern is formed is 17°, and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is 28 °.

4. Pattern formation

In Example 20, the substrate on which the first parallel line pattern was formed was placed on a hot plate at 120 ° C, and the heating was performed by heating for 1 hour.

After the cleaning by heating, the second linear liquid was applied and dried in the same manner as in Example 20 to form a second parallel line pattern.

In this manner, a functional pattern in a grid shape in which the first parallel line pattern and the second parallel line pattern intersect each other at right angles is formed. network The size of the grid-shaped functional pattern is 50 mm × 50 mm.

(Example 23)

In the same manner as in Example 22 except that the cleaning by heating was replaced with the following washing by electromagnetic waves, a grid-like pattern was formed.

<washing by electromagnetic waves>

As a cleaning by electromagnetic waves, cleaning by a flash lamp is performed.

The xenon flash system "SINTERON 2000" was used, and the xenon flash was irradiated once with a pulse width of 500 μsec and an applied voltage of 3.8 kV, and the area in the formation region including the first parallel line pattern was made. Wash.

(Example 24)

In the same manner as in Example 22 except that the washing by heating was replaced with the following washing with a solvent, a grid-like pattern was formed.

<washing by solvent>

The area in the formation region including the first parallel line pattern was washed by immersion in 2-propanol for 10 minutes.

(Embodiment 25)

1. Modulation of ink

As the ink, ink 1 is used.

2. Modulation of the substrate

As the substrate, a substrate 2 (surface energy E = 48 mN/m) was used.

3. Determination of surface energy and contact angle

The substrate 1 of Example 20 was replaced with the substrate 2, and was measured in the same manner as in Example 20. As a result, the surface energy C in the region where the first parallel line pattern was formed was 56 mN/m. The contact angle F of the second linear liquid in the region where the first parallel line pattern is formed is 17°, and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is 28 °.

4. Pattern formation

In the application of the ink, the liquid application amount per unit length of the second linear liquid in the formation region of the first parallel line pattern is adjusted to the formation region of the first parallel line pattern. The same procedure as in Example 20 was carried out, except that the amount of the liquid to be applied was 70%.

In this manner, a functional pattern in a grid shape in which the first parallel line pattern and the second parallel line pattern intersect each other at right angles is formed. The overall size of the grid-like functional pattern is 50 mm × 50 mm.

(Example 26)

1. Modulation of ink

As the ink, ink 1 is used.

2. Modulation of the substrate

As the substrate, a substrate 3 made of a PET substrate having a surface energy E of 56 mN/m by easy post-processing (surface treatment) was used.

3. Determination of surface energy and contact angle

First, an aqueous dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight) was applied onto a substrate 3 by wire bar #7, and dried to produce a function. The flat surface of the material (silver nanoparticle). After measuring the surface energy of the flat surface, the result was 61 mN/m. This value is used as a surface energy D of a flat coating surface which is obtained by applying and drying a liquid having the same composition as that of the first linear liquid.

Further, the substrate 1 of Example 20 was replaced with the substrate 3, and was measured in the same manner as in Example 20. As a result, the surface energy C in the region where the first parallel line pattern was formed was 56 mN/ m, the contact angle F of the second linear liquid in the region where the first parallel line pattern is formed is 15°, and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is It is 19°.

4. Pattern formation

In the same manner as in Example 20 except that the substrate 1 was replaced with the substrate 3, a functional pattern in a grid shape was formed.

(Example 27)

1. Modulation of ink

The ink 4 composed of the following composition was prepared.

‧ Silver nanoparticle aqueous dispersion 1 (silver nanoparticle: 40% by weight): 1.75 wt%

‧ Diethylene glycol monobutyl ether: 20% by weight

‧Pure water: Residue

2. Modulation of the substrate

As the substrate, the substrate 1 (surface energy E = 52 mN/m) was used.

3. Determination of contact angle

The contact angle measuring device "DM-501" manufactured by Kyowa Interface Chemical Co., Ltd. was used, and the contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C) outside the formation region of the first parallel line pattern was measured. As a result, the contact angle H was 5°. Further, the value after 5 seconds elapsed after dropping diethylene glycol monobutyl ether was employed.

4. Pattern formation

In the same manner as in Example 20 except that the ink 1 was replaced with the ink 4, a functional pattern in a grid shape was formed.

(Embodiment 28)

1. Modulation of ink

As the ink, ink 1 is used.

2. Modulation of the substrate

As the substrate, a substrate 2 (surface energy E = 48 mN/m) was used.

3. Determination of surface energy and contact angle

The substrate 1 of Example 20 was replaced with the substrate 2, and was measured in the same manner as in Example 20. As a result, the surface energy C in the region where the first parallel line pattern was formed was 56 mN/m. The contact angle F of the second linear liquid in the region where the first parallel line pattern is formed is 17°, and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is 28 °.

4. Pattern formation

In the same manner as in Example 20 except that the substrate 1 was replaced with the substrate 2, a functional pattern in a grid shape was formed.

(Comparative Example 2)

1. Modulation of ink

The ink 3 composed of the following composition was prepared.

‧ Silver nanoparticle particle dispersion 3 (silver nanoparticle: 40% by weight): 1.75 wt%

‧矽 surfactant (BYK-348 by BYK): 0.01% by weight

‧Pure water: Residue

Further, the aqueous dispersion 3 of the silver nanoparticles and the aqueous dispersions 1 and 2 of the silver nanoparticles are different in dispersant.

2. Modulation of the substrate

As the substrate, a substrate 2 (surface energy E = 48 mN/m) was used.

3. Determination of surface energy and contact angle

The ink 1 of Example 20 was replaced with the ink 3, and the substrate 1 was further replaced with the substrate 2, and the measurement was carried out in the same manner as in Example 20, and as a result, in the formation region of the first parallel line pattern. The surface energy C is 61 mN/m, and the contact angle F of the second linear liquid in the region where the first parallel line pattern is formed is 12°, and the second line outside the formation region of the first parallel line pattern The contact angle G of the liquid is 29°.

4. Pattern formation

In Embodiment 20, the ink 1 is replaced with the ink 3, and further A substrate-like functional pattern was formed in the same manner as in Example 20 except that the substrate 1 was replaced with the substrate 2.

(Example 29)

1. Modulation of ink

As the ink, the ink 4 is used.

2. Modulation of the substrate

As the substrate, a substrate 2 (surface energy E = 48 mN/m) was used.

3. Determination of contact angle

The contact angle measuring device "DM-501" manufactured by Kyowa Interface Chemical Co., Ltd. was used, and the contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C) outside the formation region of the first parallel line pattern was measured. As a result, the contact angle H was 8°. Further, the value after 5 seconds elapsed after dropping diethylene glycol monobutyl ether was employed.

4. Pattern formation

In the same manner as in Example 27 except that the substrate 1 was replaced with the substrate 2 in the same manner as in Example 27, a grid-like functional pattern was formed.

<Measurement of average interval A and average interval B>

In the mesh-like functional pattern obtained in Examples 20 to 30, the average of the intervals between the line segments constituting the second parallel line pattern in the formation region of the first parallel line pattern The interval A is obtained by taking the average value of the intervals measured at the measurement sites A ₁ to A ₇ of the total of seven locations described in FIG. 6 . Further, the average interval B outside the formation region of the first parallel line pattern is determined as the interval between the line segments constituting the two parallel line patterns, and is measured in a total of five places described in FIG. The average of the measured intervals at the places B ₁ to B ₅ was taken out. Further, based on the values of the average interval A and the average interval B, the value of B/A in the above formula (1) is obtained.

By taking out the value of this B/A, it is possible to determine whether or not the above formula (1) is satisfied. In other words, it can be said that it is possible to determine whether or not the adjustment to satisfy the above formula (1) is achieved.

<Evaluation method>

‧ low visual recognition evaluation method

The grid-like functional patterns obtained in Examples 20 to 30 were visually observed and evaluated based on the following evaluation criteria.

[evaluation benchmark]

A: It is impossible to visually recognize things like periodic patterns, but cover all visually uniform.

B: It is possible to visually recognize something like a periodic pattern.

‧ Evaluation method for uneven direction of resistance value

With respect to the grid-like functional patterns obtained in Examples 20 to 30, the direction unevenness of the resistance values was evaluated by the following method.

Cutting a short length of 50 mm and a width of 10 mm parallel to the direction of the first parallel line pattern (first direction), and setting the measurement by silver paste at both ends of the long side (that is, the short side) The resistance between the terminals of the short-pick was measured by an electric machine using an electrode. Similarly, a short length of 50 mm and a width of 10 mm parallel to the direction of the second parallel line pattern (the second direction) is cut out, and the resistance between the terminals is also measured by the tester, and for the first direction. The ratio of the resistance in the second direction was evaluated. Specifically, the ratio of the resistance is the absolute value of the difference between the "resistance in the second direction" and the "resistance in the first direction" divided by the value of the "resistance in the first direction", and The percentage is shown as a presenter.

As a certain criterion, it can be evaluated that if the ratio of the electric resistance is 10% or less, it is practically preferable, and if the ratio of the electric resistance exceeds 10%, it is not preferable in practical use.

The above results are shown in Table 7.

<Evaluation>

According to Table 7, it can be seen that in Examples 20 to 27 in which the average interval A and the average interval B satisfy "0.9≦B/A≦1.1" of the formula (1), It is excellent in low visibility and also prevents uneven orientation of resistance values. On the other hand, in Examples 28 to 30 in which such adjustment was not performed, the difference in visibility was poor, and the direction unevenness of the resistance value was not sufficiently prevented.

Further, with respect to the grid-like functional pattern of Example 22 and the grid-like functional pattern of Example 29, optical micrographs are shown in Figs. 25(b) and 25(a), respectively. In each of the photographs, 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). From the comparison of the photographs of these, it is also known that, according to the present invention, it is excellent in low visibility. Further, in the first direction and in the second direction, the difference in length of the conductive path was not observed, and it was found that the direction of the resistance value was prevented from being uneven.

According to the above results, it is possible to confirm the validity of the average interval A and the average interval B to be adjusted so as to satisfy the equation (1) "0.9≦B/A≦1.1".

In the examples 20 and 21, the difference (|CE|) between the surface energy C in the formation region of the first parallel line pattern and the surface energy E outside the formation region of the first parallel line pattern is set. The adjustment is 5mN/m or less, or by "will be in the formation area of the first parallel line pattern" The difference between the contact angle F between the second linear liquid and the contact angle G of the second linear liquid outside the region where the first parallel line pattern is formed is 10° or less, and the average interval is A and the average interval B satisfy the formula (1) "0.9≦B/A≦1.1". Here, as an example, an example in which the surface energy or the contact angle is adjusted by the surface treatment of the substrate or the ink composition is shown.

In the examples 22 to 24, the adjustment of the region including the formation region of the first parallel line pattern before the second linear liquid is applied is performed after the formation of the first parallel line pattern. In order to make the average interval A and the average interval B satisfy the formula (1) "0.9≦B/A≦1.1". In Example 22, washing by heating was used, and in Example 23, washing by electromagnetic waves was used, and in Example 24, washing by solvent was used.

In the twenty-fifth embodiment, the amount of the liquid per unit length of the second linear liquid in the formation region of the first parallel line pattern and the second portion outside the formation region of the first parallel line pattern are used. The liquid supply amount per unit length of the linear liquid is adjusted to be different from each other, so that the average interval A and the average interval B satisfy the formula (1) "0.9 ≦ B / A ≦ 1.1".

In the twenty-sixth embodiment, the difference (|CE|) between the surface energy C in the formation region of the first parallel line pattern and the surface energy E outside the formation region of the first parallel line pattern is set to 5 mN. /m or less" is adjusted by "the contact angle F of the second linear liquid in the region where the first parallel line pattern is formed and the second outside the formation region of the first parallel line pattern" The difference between the contact angles G of the linear liquids is set to 10° or less, or the surface of the flat coated surface formed by applying a liquid having the same composition as that of the first linear liquid and drying it. The difference between the energy D and the surface energy E outside the formation region of the first parallel line pattern (|DE|) is adjusted to be 5 mN/m or less, so that the average interval A and the average interval B satisfy the formula (1). ) "0.9≦B/A≦1.1".

In the embodiment 27, the contact angle of the solvent having the highest boiling point in the solvent in the second linear liquid outside the formation region of the first parallel line pattern is adjusted to be 6 or less. Therefore, the average interval A and the average interval B satisfy the equation (1) "0.9≦B/A≦1.1".

1‧‧‧Substrate

2‧‧‧1st linear liquid

2'‧‧‧Other linear liquids

2a~2f, 2a’~2f’‧‧‧ hit position

7‧‧‧Drop ejection device

71‧‧‧Inkjet head

72a~72f‧‧‧Nozzles

D‧‧‧ Relative movement direction of the droplet discharge device relative to the substrate

Claims (27)

A pattern forming method for discharging a liquid containing a functional material from the substrate by a plurality of nozzles of the droplet discharge device while relatively moving the droplet discharge device relative to the substrate In the case of the formed droplets, at least one set of droplets adjacent to each other which are merged into one object on the substrate, which is in the direction of relative movement and the direction orthogonal to the relative movement direction The upper space is spaced apart for arrangement, and the droplets of the droplets and one or both of the intervals are adjusted in such a manner that the droplets are combined into one. The droplets are combined and dried into a formed linear liquid to deposit the aforementioned functional material at the edge of the linear liquid and form a pattern containing the functional material. The pattern forming method according to the first aspect of the invention, wherein in the formation of the linear liquid, a plurality of pixel groups arranged in parallel with respect to a nozzle row of the droplet discharge device are plural. The droplet group given by the nozzle is provided as a complex array in a direction intersecting the nozzle row, and the droplets of the complex array are combined to form one, and the foregoing is formed to extend in a direction crossing the nozzle row. Linear liquid. The pattern forming method according to the first or second aspect of the invention, wherein the linearity of the edge portion of the linear liquid formed by combining the droplets is improved One or both of the droplet capacity and the aforementioned interval are adjusted. The pattern forming method according to the first or second aspect of the invention, wherein the total liquid droplet volume V[pL] discharged from the one nozzle is used to form one of the linear liquids. And the nozzle column resolution R[npi] in a direction orthogonal to the aforementioned relative moving direction of the plurality of nozzles, and the product V‧R[pL‧npi] of the two is adjusted to 4.32×10 ⁴ [ pL‧npi] The range below 5.18 × 10 ⁵ [pL‧npi]. The pattern forming method according to the first or second aspect of the invention, wherein the droplet volume is adjusted by adjusting the gradation. The pattern forming method according to the first or second aspect of the invention, wherein the contact angle of the liquid droplets discharged from the liquid droplet discharging device on the substrate is 10 [°] or more and 30 [°] The range below. The pattern forming method according to the first or second aspect of the invention, wherein the one or more of the linear liquids are formed by one pass of the relative movement. The pattern forming method according to the first or second aspect of the invention, wherein the linear liquid which is parallel to each other is formed by one pass of the relative movement, The interval of the linear liquid is adjusted to suppress mutual interference when the adjacent linear liquid is dried. The pattern forming method according to the first or second aspect of the invention, wherein the linear liquid is formed in a plurality of parallel liquids which are parallel to each other by the relative movement. Adjusting the interval of the liquid, by the time interval for discharging the droplets from each of the nozzles, and the relative position of the droplet discharge device relative to the substrate The relative movement speed, one or both of these adjustments are made. The pattern forming method according to the first or second aspect of the invention, wherein the linear liquid is formed in a plurality of parallel liquids which are parallel to each other by the relative movement. The interval between the liquids is adjusted to 400 [μm] or more. The pattern forming method according to the first or second aspect of the invention, wherein the one of the linear liquids is formed to be adjacent to each other in a manner of promoting the combination of the liquid droplets. The maximum discharge time difference Δt _max of the liquid containing the functional material discharged from each of the nozzles is adjusted to 200 [ms] or less. The pattern forming method according to the first or second aspect of the invention, wherein the first linear liquid is applied to the substrate, and the first linear liquid is dried. The functional material is selectively deposited on the edge portion to form a first parallel line pattern composed of two line segments including the functional material, and then on the substrate, with the first parallel line The second linear liquid is applied to the pattern forming region so as to intersect with each other, and the functional material is selectively deposited on the edge portion during drying of the second linear liquid. The second parallel line pattern formed by the two line segments of the functional material forms a pattern in which the first parallel line pattern and the second parallel line pattern intersect at at least one intersection. The pattern forming method according to claim 12, wherein the interval between the two line segments constituting the second parallel line pattern is an average interval in a region where the first parallel line pattern is formed. A and the average interval B outside the formation region of the first parallel line pattern satisfy the following formula (1), and are adjusted: 0.9 ≦ B / A ≦ 1.1 (1). The pattern forming method according to claim 13, wherein the surface energy in the formation region of the first parallel line pattern and the first parallel line pattern are adjusted to satisfy the above formula (1). The difference between the surface energies outside the formation region is set to 5 mN/m or less. The pattern forming method according to claim 13, wherein the functional material contained in the first linear liquid is applied and dried to satisfy the adjustment of the above formula (1). The difference between the surface energy of the coated surface and the surface energy outside the region where the first parallel line pattern is formed is 5 mN/m or less. The pattern forming method according to claim 13, wherein the adjustment of the formula (1) is performed by contacting the second linear liquid in the formation region of the first parallel line pattern. The difference between the angle and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern is 10 or less. The pattern forming method according to claim 13, wherein the functional material contained in the first linear liquid is applied and dried to satisfy the adjustment of the above formula (1). The difference between the contact angle of the second linear liquid at the flat coating surface and the contact angle of the second linear liquid outside the formation region of the first parallel line pattern is 10 or less. The method for forming a pattern according to claim 13, wherein the adjustment to satisfy the expression (1) is performed in the second linear liquid outside the formation region of the first parallel line pattern. The contact angle of the solvent having the highest boiling point in the solvent is set to 6 or less. The pattern forming method according to claim 13, wherein the second linear liquid in the formation region of the first parallel line pattern is adjusted to satisfy the adjustment of the above formula (1) The liquid application amount per unit length and the liquid application amount per unit length of the second linear liquid outside the formation region of the first parallel line pattern are different from each other. The pattern forming method according to claim 13, wherein the adjustment to satisfy the above formula (1) is performed after the first parallel line pattern is formed, before the second linear liquid is applied. The region in the formation region including the first parallel line pattern is washed. The pattern forming method according to claim 20, wherein the cleaning is performed by washing by heating, washing by electromagnetic waves, washing by a solvent, and gas. Washing by one or a combination of two or more selected from the washing and the washing by the plasma. Such as the pattern shape described in item 1 or 2 of the patent application scope In the method of drying, when the linear liquid is dried, a treatment for promoting drying is applied. The method of forming a pattern according to the first or second aspect of the invention, wherein the content of the functional material of the liquid discharged from the droplet discharge device is 0.01% by weight or more and 1% by weight or less. . The pattern forming method according to the first or second aspect of the invention, wherein the functional material is a conductive material or a conductive material precursor. A transparent conductive film substrate characterized by being provided on a surface of a substrate and having a transparent pattern formed by the pattern forming method according to any one of claims 1 to 24. Conductive film. An image display device comprising a transparent conductive film substrate as described in claim 25 of the patent application. An image display electronic device characterized by comprising the image display device as described in claim 26 of the patent application.